U.S. patent application number 14/110334 was filed with the patent office on 2015-08-20 for thermally conductive blended polymer compositions with improved flame retardancy.
This patent application is currently assigned to SABIC Innovative Plastics IP B.V.. The applicant listed for this patent is Mingcheng Guo, Frans Mercx. Invention is credited to Mingcheng Guo, Frans Mercx.
Application Number | 20150232664 14/110334 |
Document ID | / |
Family ID | 50236465 |
Filed Date | 2015-08-20 |
United States Patent
Application |
20150232664 |
Kind Code |
A1 |
Guo; Mingcheng ; et
al. |
August 20, 2015 |
THERMALLY CONDUCTIVE BLENDED POLYMER COMPOSITIONS WITH IMPROVED
FLAME RETARDANCY
Abstract
Disclosed herein are methods and compositions of thermally
conductive polymers with improved flame retardancy. The resulting
compositions can be used in the manufacture of articles while still
retaining the advantageous physical properties of thermally
conductive polymers with improved flame retardancy. This abstract
is intended as a scanning tool for purposes of searching in the
particular art and is not intended to be limiting of the present
invention.
Inventors: |
Guo; Mingcheng; (Shanghai,
CN) ; Mercx; Frans; (Halsteren, NL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Guo; Mingcheng
Mercx; Frans |
Shanghai
Halsteren |
|
CN
NL |
|
|
Assignee: |
SABIC Innovative Plastics IP
B.V.
Bergen OP Zoom
NL
|
Family ID: |
50236465 |
Appl. No.: |
14/110334 |
Filed: |
September 7, 2012 |
PCT Filed: |
September 7, 2012 |
PCT NO: |
PCT/CN2012/081117 |
371 Date: |
May 8, 2015 |
Current U.S.
Class: |
252/75 |
Current CPC
Class: |
C08L 23/02 20130101;
C08L 67/02 20130101; C08K 3/22 20130101; C09K 5/14 20130101; C08L
81/02 20130101; C08K 2201/001 20130101; C08L 23/02 20130101; C08L
67/02 20130101; C08K 3/22 20130101; C08L 81/02 20130101; C08K 7/14
20130101; C08K 3/04 20130101; C08L 77/02 20130101; C08L 77/02
20130101; C08K 7/14 20130101; C08L 81/02 20130101; C08K 3/22
20130101; C08K 7/14 20130101; C08L 81/02 20130101; C08K 3/22
20130101; C08L 81/02 20130101; C08K 3/22 20130101; C08K 3/04
20130101; C08K 3/042 20170501; C08L 77/02 20130101 |
International
Class: |
C08L 77/02 20060101
C08L077/02; C09K 5/14 20060101 C09K005/14 |
Claims
1. A thermally conductive polymer composition comprising: (a) from
about 20 wt % to about 60 wt % of an organic polymer comprising
polyamide, polyester, or polyolefin; (b) from about 30 wt % to
about 70 wt % of a thermal conductive additive comprising magnesium
hydroxide or aluminum oxide hydroxide; and (c) from about 1 wt % to
about 10 wt % of a polyarylene sulfide; wherein all weight percent
values are based on the total weight of the composition; and
wherein the composition exhibits a flame retardancy greater than
that of an otherwise identical composition without the polyarylene
sulfide.
2. The composition of claim 1, further comprising from about 1 wt %
to about 30 wt % of a reinforcing filler.
3. The composition of claim 2, wherein the reinforcing filler is
glass fiber.
4. The composition of claim 1, wherein the thermal conductive
additive is magnesium hydroxide.
5. The composition of claim 1, wherein the thermal conductive
additive is aluminum oxide hydroxide.
6. The composition of claim 5, wherein the aluminum oxide hydroxide
is boehmite (.gamma.-AlO(OH)).
7. (canceled)
8. The composition of claim 1, comprising a high-thermal conductive
filler selected from AlN (aluminum nitride), Al.sub.4C.sub.3
(aluminum carbide), Al.sub.20.sub.3 (aluminum oxide), BN (Boron
nitride), AlON (aluminum oxynitride), MgSiN.sub.2 (magnesium
silicon nitride), SiC (silicon carbide), Si.sub.3N.sub.4 (Silicon
nitride), graphite, expanded graphite, graphene, and carbon
fiber.
9. (canceled)
10. (canceled)
11. The composition of claim 8, wherein the high-thermal conductive
filler has a thermal conductivity greater than or equal to about 10
W/mK.
12. The composition of claim 8, wherein the high-thermal conductive
filler has a thermal conductivity greater than or equal to about 25
W/mK.
13. The composition of claim 8, wherein the high-thermal conductive
filler is present in an amount from about 10 wt % to about 25 wt
%.
14. The composition of claim 8, wherein the high-thermal conductive
filler is present in an amount from about 12 wt % to about 18 wt
%.
15. (canceled)
16. (canceled)
17. The composition of claim 1, wherein the polyarylene sulfide
comprises a plurality of structural units of the formula:
##STR00009## wherein for each structural unit, each Q.sup.1 and
each Q.sup.2 is independently hydrogen, halogen, primary or
secondary lower alkyl, phenyl, haloalkyl, aminoalkyl,
hydrocarbonoxy, or halohydrocarbonoxy wherein at least two carbon
atoms separate the halogen and oxygen atoms.
18. The composition of claim 17, wherein each Q.sup.1 is hydrogen,
alkyl, or phenyl.
19. The composition of claim 17, wherein at least one Q.sup.1 is
C.sub.1-4 alkyl.
20. The composition of claim 17, wherein each Q.sup.2 is
hydrogen.
21. The composition of claim 1, wherein the polyarylene sulfide
comprises a plurality of structural units of the formula:
##STR00010## wherein for each structural unit, each Q.sup.1 and
each Q.sup.2 is independently hydrogen, halogen, primary or
secondary lower alkyl, phenyl, haloalkyl, aminoalkyl,
hydrocarbonoxy, or halohydrocarbonoxy wherein at least two carbon
atoms separate the halogen and oxygen atoms.
22. The composition of claim 21, wherein each Q.sup.1 is hydrogen,
alkyl, or phenyl.
23. The composition of claim 21, wherein at least one Q.sup.1 is
C.sub.1-4 alkyl.
24. The composition of claim 21, wherein each Q.sup.2 is
hydrogen.
25. The composition of claim 1, wherein the polyarylene sulfide is
polyphenylene sulfide.
26. The composition of claim 1, further comprising an additive
selected from coupling agents, antioxidants, mold release agents,
UV absorbers, light stabilizers, heat stabilizers, lubricants,
plasticizers, pigments, dyes, colorants, anti-static agents,
nucleating agents, anti-drip agents, acid scavengers, and
combinations of two or more of the foregoing.
27. The composition of claim 1, wherein the composition exhibits a
VO compliant flame retardancy.
28. A method of improving the flame retardancy of a thermally
conductive polymer composition, the method comprising the step of
combining: (a) from about 20 wt % to about 60 wt % of an organic
polymer comprising polyamide, polyester, or polyolefin; (b) from
about 30 wt % to about 70 wt % of a thermal conductive additive
comprising magnesium hydroxide or aluminum oxide hydroxide; and (c)
from about 1 wt % to about 10 wt % of a polyarylene sulfide;
wherein all weight percent values are based on the total weight of
the composition; and wherein the composition exhibits a flame
retardancy greater than that of an otherwise identical composition
without the polyarylene sulfide.
29. The method of claim 28, further comprising including from about
1 wt % to about 30 wt % of a reinforcing filler.
30. (canceled)
31. The method of claim 28, further comprising including an
additive selected from coupling agents, antioxidants, mold release
agents, UV absorbers, light stabilizers, heat stabilizers,
lubricants, plasticizers, pigments, dyes, colorants, anti-static
agents, nucleating agents, anti-drip agents, acid scavengers, and
combinations of two or more of the foregoing.
32. The method of claim 28, wherein the polyarylene sulfide is
polyphenylene sulfide.
33. The method of claim 28, wherein the combining step comprises
adding the polyarylene sulfide to a mixture of the organic polymer
and the magnesium hydroxide or boehmite (.gamma.-AlO(OH)).
34. An extruded or injection molded article, comprising the product
of extrusion molding or injection molding a composition comprising:
(a) from about 20 wt % to about 60 wt % of an organic polymer
comprising polyamide, polyester, or polyolefin; (b) from about 30
wt % to about 70 wt % of a thermal conductive additive comprising
magnesium hydroxide or aluminum oxide hydroxide; and (c) from about
1 wt % to about 10 wt % of a polyarylene sulfide; wherein all
weight percent values are based on the total weight of the
composition; and wherein the composition exhibits a flame
retardancy greater than that of an otherwise identical composition
without the polyarylene sulfide.
35. The article of claim 34, further comprising from about 1 wt %
to about 30 wt % of a reinforcing filler.
36. (canceled)
37. The article of claim 34, further comprising a high-thermal
conductive filler.
38. The article of claim 34, wherein the polyarylene sulfide
comprises a plurality of structural units of the formula:
##STR00011## wherein for each structural unit, each Q.sup.1 and
each Q.sup.2 is independently hydrogen, halogen, primary or
secondary lower alkyl, phenyl, haloalkyl, aminoalkyl,
hydrocarbonoxy, or halohydrocarbonoxy wherein at least two carbon
atoms separate the halogen and oxygen atoms.
39. The article of claim 34, wherein the polyarylene sulfide is
polyphenylene sulfide.
40. The article of claim 34, further comprising an additive
selected from coupling agents, antioxidants, mold release agents,
UV absorbers, light stabilizers, heat stabilizers, lubricants,
plasticizers, pigments, dyes, colorants, anti-static agents,
nucleating agents, anti-drip agents, acid scavengers, and
combinations of two or more of the foregoing.
41. The article of claim 34, wherein the composition exhibits a VO
compliant flame retardancy.
Description
FIELD OF INVENTION
[0001] The present invention relates to organic polymer
compositions having, among other characteristics, improved flame
retardancy, and specifically to blended polymer compositions
comprising an organic polymer such as a polyamide, a polyester, or
a polyolefin; a thermally conductive filler such as magnesium
hydroxide or boehmite; and a char-forming polymer such as a
polyarylene sulfide; wherein the blended polymer composition has
improved flame retardancy without adversely affecting the thermal
conductivity of the polymer composition. Also included herein are
methods for preparing and/or using the same, as well as articles
formed from such polymer compositions.
BACKGROUND
[0002] In electronic applications, there is an increasing need for
thermal management. For example, heat build-up can lead to a
reduced product lifetime in light emitting diodes, in drivers, and
in contact housings and can also lead to reduced efficiency in
solar cells. Accordingly, compositions having poor thermal
management can yield inferior products.
[0003] Since polymers are electrical and thermal insulators,
thermally conductive fillers can be added to improve thermal
management. However, an unacceptably high content of thermally
conductive filler is typically necessary to achieve thermal
conductivities suitable for efficient heat transport through a
polymer composite. Such high content is especially undesirable in
view of conventional thermally conductive filler materials
typically being based on relatively expensive ceramics.
[0004] Further, for many electronic applications, flame retardancy
is also required. When using relatively low-cost flame-retardants,
conventional compositions typically employ phosphorus-based flame
retardants to achieve this goal. As would be appreciated by those
of skill, adding a mineral-based flame retardant to a polymer
composition reduces the total amount of thermal conductive fillers
that can be included in the composition, thereby limiting the level
of thermal conductivity that can be achieved. Thus, there is a need
for thermally conductive polymer compositions with improved flame
retardancy. This and other needs are satisfied by the disclosed
invention.
SUMMARY OF THE INVENTION
[0005] As described in more detail herein, the present invention
provides a compositions having improved flame retardancy. For
example, in one aspect, the invention relates to a thermally
conductive polymer composition comprising: from about 20 wt % to
about 60 wt % of an organic polymer selected from polyamide,
polyester, and polyolefin; from about 30 wt % to about 70 wt % of a
thermal conductive additive selected from magnesium hydroxide or
aluminum oxide hydroxide; and from about 1 wt % to about 10 wt % of
a polyarylene sulfide; wherein all weight percent values are based
on the total weight of the composition; wherein the composition
exhibits a flame retardancy greater than that of an otherwise
identical composition without the polyarylene sulfide.
[0006] In a further aspect, the invention relates to a method of
improving the flame retardancy of a thermally conductive polymer
composition, the method comprising the step of combining: from
about 20 wt % to about 60 wt % of an organic polymer selected from
polyamide, polyester, and polyolefin; from about 30 wt % to about
70 wt % of a thermal conductive additive selected from magnesium
hydroxide or aluminum oxide hydroxide; and from about 1 wt % to
about 10 wt % of a polyarylene sulfide; wherein all weight percent
values are based on the total weight of the composition; wherein
the composition exhibits a flame retardancy greater than that of an
otherwise identical composition without the polyarylene
sulfide.
[0007] In a further aspect, the invention relates to an extruded or
injection molded article, comprising the product of extrusion
molding or injection molding a composition comprising: from about
20 wt % to about 60 wt % of an organic polymer selected from
polyamide, polyester, and polyolefin; from about 30 wt % to about
70 wt % of a thermal conductive additive selected from magnesium
hydroxide or aluminum oxide hydroxide; and from about 1 wt % to
about 10 wt % of a polyarylene sulfide; wherein all weight percent
values are based on the total weight of the composition; wherein
the composition exhibits a flame retardancy greater than that of an
otherwise identical composition without the polyarylene
sulfide.
[0008] While aspects of the present invention can be described and
claimed in a particular statutory class, such as the system
statutory class, this is for convenience only and one of skill in
the art will understand that each aspect of the present invention
can be described and claimed in any statutory class. Unless
otherwise expressly stated, it is in no way intended that any
method or aspect set forth herein be construed as requiring that
its steps be performed in a specific order. Accordingly, where a
method claim does not specifically state in the claims or
descriptions that the steps are to be limited to a specific order,
it is in no way intended that an order be inferred, in any respect.
This holds for any possible non-express basis for interpretation,
including matters of logic with respect to arrangement of steps or
operational flow, plain meaning derived from grammatical
organization or punctuation, or the number or type of aspects
described in the specification.
BRIEF DESCRIPTION OF THE FIGURES
[0009] The accompanying figures, which are incorporated in and
constitute a part of this specification, illustrate several aspects
and together with the description serve to explain the principles
of the invention.
[0010] FIG. 1 shows a representative diagram of the lay-out for
compounding and melt processing.
[0011] Additional advantages of the invention will be set forth in
part in the description which follows, and in part will be obvious
from the description, or can be learned by practice of the
invention. The advantages of the invention will be realized and
attained by means of the elements and combinations particularly
pointed out in the appended claims. It is to be understood that
both the foregoing general description and the following detailed
description are exemplary and explanatory only and are not
restrictive of the invention, as claimed.
DETAILED DESCRIPTION
[0012] The present invention can be understood more readily by
reference to the following detailed description of the invention
and the Examples included therein.
[0013] Before the present compounds, compositions, articles,
systems, devices, and/or methods are disclosed and described, it is
to be understood that they are not limited to specific synthetic
methods unless otherwise specified, or to particular reagents
unless otherwise specified, as such can, of course, vary. It is
also to be understood that the terminology used herein is for the
purpose of describing particular aspects only and is not intended
to be limiting. Although any methods and materials similar or
equivalent to those described herein can be used in the practice or
testing of the present invention, example methods and materials are
now described.
[0014] Moreover, it is to be understood that unless otherwise
expressly stated, it is in no way intended that any method set
forth herein be construed as requiring that its steps be performed
in a specific order. Accordingly, where a method claim does not
actually recite an order to be followed by its steps or it is not
otherwise specifically stated in the claims or descriptions that
the steps are to be limited to a specific order, it is no way
intended that an order be inferred, in any respect. This holds for
any possible non-express basis for interpretation, including:
matters of logic with respect to arrangement of steps or
operational flow; plain meaning derived from grammatical
organization or punctuation; and the number or type of embodiments
described in the specification.
[0015] All publications mentioned herein are incorporated herein by
reference to disclose and describe the methods and/or materials in
connection with which the publications are cited.
A. DEFINITIONS
[0016] Unless defined otherwise, all technical and scientific terms
used herein have the same meaning as commonly understood by one of
ordinary skill in the art to which this invention belongs. Although
any methods and materials similar or equivalent to those described
herein can be used in the practice or testing of the present
invention, example methods and materials are now described.
[0017] As used in the specification and the appended claims, the
singular forms "a," "an," and "the" include plural referents unless
the context clearly dictates otherwise. Thus, for example,
reference to "a ketone" includes mixtures of two or more
ketones.
[0018] Ranges can be expressed herein as from one particular value,
and/or to another particular value. When such a range is expressed,
another aspect includes from the one particular value and/or to the
other particular value. Similarly, when values are expressed as
approximations, by use of the antecedent `about,` it will be
understood that the particular value forms another aspect. It will
be further understood that the endpoints of each of the ranges are
significant both in relation to the other endpoint, and
independently of the other endpoint. It is also understood that
there are a number of values disclosed herein, and that each value
is also herein disclosed as "about" that particular value in
addition to the value itself. For example, if the value "10" is
disclosed, then "about 10" is also disclosed. It is also understood
that each unit between two particular units are also disclosed. For
example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are
also disclosed.
[0019] As used herein, the terms "about" and "at or about" mean
that the amount or value in question can be the value designated,
or a value approximately or about the same as the amount or value
in question. It is generally understood, as used herein, that it is
the nominal value indicated .+-.10% variation unless otherwise
indicated or inferred. The term is intended to convey that similar
values promote equivalent results or effects recited in the claims.
That is, it is understood that amounts, sizes, formulations,
parameters, and other quantities and characteristics are not and
need not be exact, but may be approximate and/or larger or smaller,
as desired, reflecting tolerances, conversion factors, rounding
off, measurement error and the like, and other factors known to
those of skill in the art. In general, an amount, size,
formulation, parameter or other quantity or characteristic is
"about" or "approximate" whether or not expressly stated to be
such. It is understood that where "about" is used before a
quantitative value, the parameter also includes the specific
quantitative value itself, unless specifically stated
otherwise.
[0020] As used herein, the terms "optional" or "optionally" means
that the subsequently described event or circumstance can or cannot
occur, and that the description includes instances where said event
or circumstance occurs and instances where it does not. For
example, the phrase "optionally substituted alkyl" means that the
alkyl group can or cannot be substituted and that the description
includes both substituted and unsubstituted alkyl groups.
[0021] Disclosed are the components to be used to prepare the
compositions of the invention as well as the compositions
themselves to be used within the methods disclosed herein. These
and other materials are disclosed herein, and it is understood that
when combinations, subsets, interactions, groups, etc. of these
materials are disclosed that while specific reference of each
various individual and collective combinations and permutation of
these compounds cannot be explicitly disclosed, each is
specifically contemplated and described herein. For example, if a
particular compound is disclosed and discussed and a number of
modifications that can be made to a number of molecules including
the compounds are discussed, specifically contemplated is each and
every combination and permutation of the compound and the
modifications that are possible unless specifically indicated to
the contrary. Thus, if a class of molecules A, B, and C are
disclosed as well as a class of molecules D, E, and F and an
example of a combination molecule, A-D is disclosed, then even if
each is not individually recited each is individually and
collectively contemplated meaning combinations, A-E, A-F, B-D, B-E,
B-F, C-D, C-E, and C-F are considered disclosed. Likewise, any
subset or combination of these is also disclosed. Thus, for
example, the sub-group of A-E, B-F, and C-E would be considered
disclosed. This concept applies to all aspects of this application
including, but not limited to, steps in methods of making and using
the compositions of the invention. Thus, if there are a variety of
additional steps that can be performed it is understood that each
of these additional steps can be performed with any specific aspect
or combination of aspects of the methods of the invention.
[0022] References in the specification and concluding claims to
parts by weight, of a particular element or component in a
composition or article, denote the weight relationship between the
element or component and any other elements or components in the
composition or article for which a part by weight is expressed.
Thus, in a compound containing 2 parts by weight of component X and
5 parts by weight component Y, X and Y are present at a weight
ratio of 2:5, and are present in such ratio regardless of whether
additional components are contained in the compound.
[0023] A weight percent of a component, unless specifically stated
to the contrary, is based on the total weight of the formulation or
composition in which the component is included. For example if a
particular element or component in a composition or article is said
to have 8% weight, it is understood that this percentage is
relation to a total compositional percentage of 100%.
[0024] The term "alkyl group" as used herein is a branched or
unbranched saturated hydrocarbon group of 1 to 24 carbon atoms,
such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,
t-butyl, pentyl, hexyl, heptyl, octyl, decyl, tetradecyl,
hexadecyl, eicosyl, tetracosyl and the like. A "lower alkyl" group
is an alkyl group containing from one to six carbon atoms.
[0025] The term "alkoxy" as used herein is an alkyl group bound
through a single, terminal ether linkage; that is, an "alkoxy"
group can be defined as --OR where R is alkyl as defined above. A
"lower alkoxy" group is an alkoxy group containing from one to six
carbon atoms.
[0026] The term "alkenyl group" as used herein is a hydrocarbon
group of from 2 to 24 carbon atoms and structural formula
containing at least one carbon-carbon double bond. Asymmetric
structures such as (AB)C.dbd.C(CD) are intended to include both the
E and Z isomers. This can be presumed in structural formulae herein
wherein an asymmetric alkene is present, or it can be explicitly
indicated by the bond symbol C.
[0027] The term "alkynyl group" as used herein is a hydrocarbon
group of 2 to 24 carbon atoms and a structural formula containing
at least one carbon-carbon triple bond.
[0028] The term "aryl group" as used herein is any carbon-based
aromatic group including, but not limited to, benzene, naphthalene,
etc. The term "aromatic" also includes "heteroaryl group," which is
defined as an aromatic group that has at least one heteroatom
incorporated within the ring of the aromatic group. Examples of
heteroatoms include, but are not limited to, nitrogen, oxygen,
sulfur, and phosphorus. The aryl group can be substituted or
unsubstituted. The aryl group can be substituted with one or more
groups including, but not limited to, alkyl, alkynyl, alkenyl,
aryl, halide, nitro, amino, ester, ketone, aldehyde, hydroxy,
carboxylic acid, or alkoxy.
[0029] The term "cycloalkyl group" as used herein is a non-aromatic
carbon-based ring composed of at least three carbon atoms. Examples
of cycloalkyl groups include, but are not limited to, cyclopropyl,
cyclobutyl, cyclopentyl, cyclohexyl, etc. The term
"heterocycloalkyl group" is a cycloalkyl group as defined above
where at least one of the carbon atoms of the ring is substituted
with a heteroatom such as, but not limited to, nitrogen, oxygen,
sulphur, or phosphorus.
[0030] The term "aralkyl" as used herein is an aryl group having an
alkyl, alkynyl, or alkenyl group as defined above attached to the
aromatic group. An example of an aralkyl group is a benzyl
group.
[0031] The term "hydroxyalkyl group" as used herein is an alkyl,
alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or
heterocycloalkyl group described above that has at least one
hydrogen atom substituted with a hydroxyl group.
[0032] The term "alkoxyalkyl group" is defined as an alkyl,
alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or
heterocycloalkyl group described above that has at least one
hydrogen atom substituted with an alkoxy group described above.
[0033] The term "ester" as used herein is represented by the
formula --C(O)OA, where A can be an alkyl, halogenated alkyl,
alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl,
heterocycloalkyl, or heterocycloalkenyl group described above.
[0034] The term "carbonate group" as used herein is represented by
the formula --OC(O)OR, where R can be hydrogen, an alkyl, alkenyl,
alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or
heterocycloalkyl group described above.
[0035] The term "carboxylic acid" as used herein is represented by
the formula --C(O)OH.
[0036] The term "aldehyde" as used herein is represented by the
formula --C(O)H.
[0037] The term "keto group" as used herein is represented by the
formula --C(O)R, where R is an alkyl, alkenyl, alkynyl, aryl,
aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group
described above.
[0038] The term "carbonyl group" as used herein is represented by
the formula C.dbd.O.
[0039] The term "ether" as used herein is represented by the
formula AOA.sup.1, where A and A.sup.1 can be, independently, an
alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl,
cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl
group described above.
[0040] The term "sulfo-oxo group" as used herein is represented by
the formulas --S(O).sub.2R, --OS(O).sub.2R, or, --OS(O).sub.2OR,
where R can be hydrogen, an alkyl, alkenyl, alkynyl, aryl, aralkyl,
cycloalkyl, halogenated alkyl, or heterocycloalkyl group described
above.
[0041] Each of the materials disclosed herein are either
commercially available and/or the methods for the production
thereof are known to those of skill in the art.
[0042] It is understood that the compositions disclosed herein have
certain functions. Disclosed herein are certain structural
requirements for performing the disclosed functions, and it is
understood that there are a variety of structures that can perform
the same function that are related to the disclosed structures, and
that these structures will typically achieve the same result.
B. THERMALLY CONDUCTIVE, FLAME-RETARDANT BLENDED POLYMER
COMPOSITIONS
[0043] As briefly described above, the present disclosure provides
blended polymer compositions having improved flame retardancy. In
various aspects, the blended polymer compositions of the present
invention comprise an organic polymer selected from polyamides,
polyesters or polyolefins; a thermally conductive, flame retardant
filler such as magnesium hydroxide or boehmite; and a char-forming
polymer such as a polyarylene sulfide. It is understood and herein
contemplated that the disclosed blended polymer compositions, in
one aspect, have improved flame retardancy relative to blends that
do not contain the polyarylene sulfide. In one aspect, the blended
polymer composition may optionally further comprise a reinforcing
filler, such as, for example, glass fibers. In various further
aspects, the blended polymer composition further comprises a high
thermally conductive filler, such as, for example, graphite. The
disclosed polymer compositions, in a further aspect, provide
improved flame retardancy characteristics while substantially
retaining thermal conductivity compared to blends that do contain
the polyarylene sulfide.
[0044] Moreover, because the disclosed compositions show improved
flame retardancy relative to blended polymer compositions that do
not contain the polyarylene sulfide, also disclosed herein are
methods of increasing the flame retardancy of blended polymer
composition comprising an organic polymer selected from a
polyamide, a polyester or a polyolefin; a filler such as magnesium
hydroxide or boehmite; and a char-forming polymer such as a
polyarylene sulfide, comprising substituting a portion of the
organic polymer with the polyarylene sulfide.
[0045] In one aspect, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: from about 20 wt % to about 60 wt % of an organic
polymer selected from polyamide, polyester, and polyolefin; from
about 30 wt % to about 70 wt % of a thermal conductive additive
selected from magnesium hydroxide or aluminum oxide hydroxide; and
from about 1 wt % to about 10 wt % of a polyarylene sulfide;
wherein all weight percent values are based on the total weight of
the composition; wherein the composition exhibits a flame
retardancy greater than that of an otherwise identical composition
without the polyarylene sulfide.
[0046] In a further aspect, the composition comprises from about 1
wt % to about 30 wt % of a reinforcing filler, for example, glass
fiber. In a further aspect, the composition further comprises a
high-thermal conductive filler.
[0047] In a further aspect, the composition further comprises an
additive selected from coupling agents, antioxidants, mold release
agents, UV absorbers, light stabilizers, heat stabilizers,
lubricants, plasticizers, pigments, dyes, colorants, anti-static
agents, nucleating agents, anti-drip agents, acid scavengers, and
combinations of two or more of the foregoing.
[0048] In a further aspect, the composition further comprises about
0.01 wt % to about 0.50 wt % of a first anti-oxidant additive. In a
still further aspect, the composition further comprises about 0.10
wt % to about 0.40 wt % of a first anti-oxidant additive. In a yet
further aspect, the composition further comprises about 0.15 wt %
to about 0.30 wt % of a first anti-oxidant additive. In an even
further aspect, the composition further comprises about 0.10 wt %
of a first anti-oxidant additive. In a still further aspect, the
composition further comprises about 0.15 wt % of a first
anti-oxidant additive. In a yet further aspect, the composition
further comprises about 0.20 wt % of a first anti-oxidant additive.
In an even further aspect, the composition further comprises about
0.25 wt % of a first anti-oxidant additive. In a still further
aspect, the composition further comprises about 0.30 wt % of a
first anti-oxidant additive. In various aspects, the first
anti-oxidant additive is a sterically hindered phenolic
antioxidant. In a further aspect, the first anti-oxidant additive
is N,N'-hexamethylene
bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionamide].
[0049] In a further aspect, the composition further comprises about
0.01 wt % to about 0.50 wt % of a second anti-oxidant additive. In
a still further aspect, the composition further comprises about
0.10 wt % to about 0.40 wt % of a second anti-oxidant additive. In
a yet further aspect, the composition further comprises about 0.15
wt % to about 0.30 wt % of a second anti-oxidant additive. In an
even further aspect, the composition further comprises about 0.10
wt % of a second anti-oxidant additive. In a still further aspect,
the composition further comprises about 0.15 wt % of a second
anti-oxidant additive. In a yet further aspect, the composition
further comprises about 0.20 wt % of a second anti-oxidant
additive. In an even further aspect, the composition further
comprises about 0.25 wt % of a second anti-oxidant additive. In a
still further aspect, the composition further comprises about 0.30
wt % of a second anti-oxidant additive. In various aspects, the
second anti-oxidant additive is a trisarylphosphite anti-oxidant.
In a further aspect, the second anti-oxidant additive is
tris(2,4-di-tert-butylphenyl)phosphite.
[0050] In a further aspect, the composition further comprises a
compatibilizing agent. In various aspects, the composition further
comprises a compatibilizing agent present in an amount of from
about 0.1 wt % to about 5 wt %, for example, about 0.1, 0.3, 0.5,
0.7, 0.9, 1.2, 1.4, 1.6, 1.8, 2, 2.5, 3, 3.5, 4, 4.5, or 5 wt %; or
from about 0.5 wt % to about 1.0 wt %, for example, about 0.5, 0.6,
0.7, 0.8, 0.9, or 1 wt %. In other aspects, the composition further
comprises a compatibilizing agent present in an amount less than
about 0.1 wt % or greater than about 5 wt %, and the present
invention is not intended to be limited to any particular
compatibilizing agent concentration. In one aspect, when present
the composition further comprises a compatibilizing agent present
in an amount of about 0.01 weight percent to about 5 wt %, based on
the total weight of the composition. In a further aspect, the
composition further comprises a compatibilizing agent present in an
amount from about 0.1 to about 2 wt %. In a still further aspect,
the composition further comprises a compatibilizing agent present
in an amount from about 0.1 to about 0.5 wt %. In one aspect, the
composition further comprises a compatibilizing agent present in an
amount of about 0.25%, and wherein the compatibilizing agent is a
styrenic epoxy material, such as, for example, ADR-4368C. In
another aspect, the composition further comprises a compatibilizing
agent present in an amount of about 0.50%, and wherein the
compatibilizing agent is a styrenic epoxy material, such as, for
example, ADR-4368C.
[0051] In a further aspect, the composition exhibits a V0 compliant
flame retardancy. In various further aspects, the composition
exhibits a V1 compliant flame retardancy. In still further aspects,
the composition exhibits a V2 compliant flame retardancy. In
various aspects, it is understood that flame retardancy is
determined in accordance with UL-94 guidelines on calibrated
equipment on samples conditioned at 23.degree. C. and 50% relative
humidity prior to analysis.
[0052] In various aspects, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: about 43.1 wt % of a polyamide; about 40 wt % of
magnesium hydroxide; and about 6 wt % of a polyarylene sulfide;
wherein all weight percent values are based on the total weight of
the composition; wherein the composition exhibits a flame
retardancy greater than that of an otherwise identical composition
without the polyarylene sulfide.
[0053] In various aspects, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: about 39.6 wt % of a polyamide; about 47.5 wt % of
magnesium hydroxide; and about 2 wt % of a polyarylene sulfide;
wherein all weight percent values are based on the total weight of
the composition; wherein the composition exhibits a flame
retardancy greater than that of an otherwise identical composition
without the polyarylene sulfide.
[0054] In various aspects, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: about 37.6 wt % of a polyamide; about 47.5 wt % of
magnesium hydroxide; and about 4 wt % of a polyarylene sulfide;
wherein all weight percent values are based on the total weight of
the composition; wherein the composition exhibits a flame
retardancy greater than that of an otherwise identical composition
without the polyarylene sulfide.
[0055] In various aspects, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: about 35.6 wt % of a polyamide; about 47.5 wt % of
magnesium hydroxide; and about 6 wt % of a polyarylene sulfide;
wherein all weight percent values are based on the total weight of
the composition; wherein the composition exhibits a flame
retardancy greater than that of an otherwise identical composition
without the polyarylene sulfide.
[0056] In various aspects, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: about 34.1 wt % of a polyamide; about 49 wt % of
magnesium hydroxide; and about 6 wt % of a polyarylene sulfide;
wherein all weight percent values are based on the total weight of
the composition; wherein the composition exhibits a flame
retardancy greater than that of an otherwise identical composition
without the polyarylene sulfide.
[0057] In various aspects, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: about 32.1 wt % of a polyamide; about 55 wt % of
magnesium hydroxide; and about 2 wt % of a polyarylene sulfide;
wherein all weight percent values are based on the total weight of
the composition; wherein the composition exhibits a flame
retardancy greater than that of an otherwise identical composition
without the polyarylene sulfide.
[0058] In various aspects, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: about 32.1 wt % of a polyamide; about 55 wt % of
magnesium hydroxide; and about 4 wt % of a polyarylene sulfide;
wherein all weight percent values are based on the total weight of
the composition; wherein the composition exhibits a flame
retardancy greater than that of an otherwise identical composition
without the polyarylene sulfide.
[0059] In various aspects, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: about 43.1 wt % of a polyamide;
[0060] about 40 wt % of magnesium hydroxide; about 10 wt % glass
fiber; and about 6 wt % of a polyarylene sulfide; wherein all
weight percent values are based on the total weight of the
composition; wherein the composition exhibits a flame retardancy
greater than that of an otherwise identical composition without the
polyarylene sulfide.
[0061] In various aspects, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: about 39.6 wt % of a polyamide; about 47.5 wt % of
magnesium hydroxide; about 10 wt % glass fiber; and about 2 wt % of
a polyarylene sulfide; wherein all weight percent values are based
on the total weight of the composition; wherein the composition
exhibits a flame retardancy greater than that of an otherwise
identical composition without the polyarylene sulfide.
[0062] In various aspects, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: about 37.6 wt % of a polyamide; about 47.5 wt % of
magnesium hydroxide; about 10 wt % glass fiber; and about 4 wt % of
a polyarylene sulfide; wherein all weight percent values are based
on the total weight of the composition; wherein the composition
exhibits a flame retardancy greater than that of an otherwise
identical composition without the polyarylene sulfide.
[0063] In various aspects, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: about 35.6 wt % of a polyamide; about 47.5 wt % of
magnesium hydroxide; about 10 wt % glass fiber; and about 6 wt % of
a polyarylene sulfide; wherein all weight percent values are based
on the total weight of the composition; wherein the composition
exhibits a flame retardancy greater than that of an otherwise
identical composition without the polyarylene sulfide.
[0064] In various aspects, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: about 34.1 wt % of a polyamide; about 49 wt % of
magnesium hydroxide; about 10 wt % glass fiber; and about 6 wt % of
a polyarylene sulfide; wherein all weight percent values are based
on the total weight of the composition; wherein the composition
exhibits a flame retardancy greater than that of an otherwise
identical composition without the polyarylene sulfide.
[0065] In various aspects, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: about 32.1 wt % of a polyamide; about 55 wt % of
magnesium hydroxide; about 10 wt % glass fiber; and about 2 wt % of
a polyarylene sulfide; wherein all weight percent values are based
on the total weight of the composition; wherein the composition
exhibits a flame retardancy greater than that of an otherwise
identical composition without the polyarylene sulfide.
[0066] In various aspects, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: about 32.1 wt % of a polyamide; about 55 wt % of
magnesium hydroxide; about 10 wt % glass fiber; and about 4 wt % of
a polyarylene sulfide; wherein all weight percent values are based
on the total weight of the composition; wherein the composition
exhibits a flame retardancy greater than that of an otherwise
identical composition without the polyarylene sulfide.
[0067] In various aspects, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: about 34.6 wt % of a polyamide; about 45.1 wt % of
magnesium hydroxide; and about 2 wt % of a polyarylene sulfide;
wherein all weight percent values are based on the total weight of
the composition; wherein the composition exhibits a flame
retardancy greater than that of an otherwise identical composition
without the polyarylene sulfide.
[0068] In various aspects, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: about 32.6 wt % of a polyamide; about 45.1 wt % of
magnesium hydroxide; and about 4 wt % of a polyarylene sulfide;
wherein all weight percent values are based on the total weight of
the composition; wherein the composition exhibits a flame
retardancy greater than that of an otherwise identical composition
without the polyarylene sulfide.
[0069] In various aspects, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: about 28.0 wt % of a polyamide; about 45.1 wt % of
magnesium hydroxide; and about 8 wt % of a polyarylene sulfide;
wherein all weight percent values are based on the total weight of
the composition; wherein the composition exhibits a flame
retardancy greater than that of an otherwise identical composition
without the polyarylene sulfide.
[0070] In various aspects, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: about 28.4 wt % of a polyamide; about 45.1 wt % of
magnesium hydroxide; and about 8 wt % of a polyarylene sulfide;
wherein all weight percent values are based on the total weight of
the composition; wherein the composition exhibits a flame
retardancy greater than that of an otherwise identical composition
without the polyarylene sulfide.
[0071] In various aspects, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: about 28.1 wt % of a polyamide; about 45.1 wt % of
magnesium hydroxide; and about 2 wt % of a polyarylene sulfide;
wherein all weight percent values are based on the total weight of
the composition; wherein the composition exhibits a flame
retardancy greater than that of an otherwise identical composition
without the polyarylene sulfide.
[0072] In various aspects, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: about 30.6 wt % of a polyamide; about 52.6 wt % of
magnesium hydroxide; and about 4 wt % of a polyarylene sulfide;
wherein all weight percent values are based on the total weight of
the composition; wherein the composition exhibits a flame
retardancy greater than that of an otherwise identical composition
without the polyarylene sulfide.
[0073] In various aspects, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: about 30.6 wt % of a polyamide; about 52.6 wt % of
magnesium hydroxide; and about 6 wt % of a polyarylene sulfide;
wherein all weight percent values are based on the total weight of
the composition; wherein the composition exhibits a flame
retardancy greater than that of an otherwise identical composition
without the polyarylene sulfide.
[0074] In various aspects, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: about 34.6 wt % of a polyamide; about 45.1 wt % of
magnesium hydroxide; about 17.5 wt % of a graphite; and about 2 wt
% of a polyarylene sulfide; wherein all weight percent values are
based on the total weight of the composition; wherein the
composition exhibits a flame retardancy greater than that of an
otherwise identical composition without the polyarylene
sulfide.
[0075] In various aspects, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: about 32.6 wt % of a polyamide; about 45.1 wt % of
magnesium hydroxide; about 17.5 wt % of a graphite; and about 4 wt
% of a polyarylene sulfide; wherein all weight percent values are
based on the total weight of the composition; wherein the
composition exhibits a flame retardancy greater than that of an
otherwise identical composition without the polyarylene
sulfide.
[0076] In various aspects, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: about 28.0 wt % of a polyamide; about 45.1 wt % of
magnesium hydroxide; about 17.5 wt % of a graphite; and about 8 wt
% of a polyarylene sulfide; wherein all weight percent values are
based on the total weight of the composition; wherein the
composition exhibits a flame retardancy greater than that of an
otherwise identical composition without the polyarylene
sulfide.
[0077] In various aspects, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: about 28.4 wt % of a polyamide; about 45.1 wt % of
magnesium hydroxide; about 17.5 wt % of a graphite; about 0.25 wt %
of a compatibilizing agent; and about 8 wt % of a polyarylene
sulfide; wherein all weight percent values are based on the total
weight of the composition; wherein the composition exhibits a flame
retardancy greater than that of an otherwise identical composition
without the polyarylene sulfide.
[0078] In various aspects, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: about 28.1 wt % of a polyamide; about 45.1 wt % of
magnesium hydroxide; about 17.5 wt % of a graphite; about 0.50 wt %
of a compatibilizing agent; and about 2 wt % of a polyarylene
sulfide; wherein all weight percent values are based on the total
weight of the composition; wherein the composition exhibits a flame
retardancy greater than that of an otherwise identical composition
without the polyarylene sulfide.
[0079] In various aspects, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: about 30.6 wt % of a polyamide; about 52.6 wt % of
magnesium hydroxide; about 12.0 wt % of a graphite; and about 4 wt
% of a polyarylene sulfide; wherein all weight percent values are
based on the total weight of the composition; wherein the
composition exhibits a flame retardancy greater than that of an
otherwise identical composition without the polyarylene
sulfide.
[0080] In various aspects, the invention relates to blended polymer
compositions with improved flame retardancy, the compositions
comprising: about 30.6 wt % of a polyamide; about 52.6 wt % of
magnesium hydroxide; about 12.0 wt % of a graphite; and about 6 wt
% of a polyarylene sulfide; wherein all weight percent values are
based on the total weight of the composition; wherein the
composition exhibits a flame retardancy greater than that of an
otherwise identical composition without the polyarylene
sulfide.
C. CHAR-FORMING POLYMER
[0081] In one aspect, the disclosed blended polymer compositions
with improved heat resistance of the present invention comprise a
char-forming polymer. In one aspect, char-forming polymers can be
polyarylene sulfide polymers. In various further aspects, the
char-forming polymer is polyphenylene sulfide
[0082] In various aspects, the composition comprises a polyarylene
sulfide as the char-forming polymer. The term polyarylene sulfide
polymer includes polyphenylene sulfide (PPS), polyarylene sulfide
ionomers, polyarylene sulfide copolymers, polyarylene sulfide graft
copolymers, block copolymers of polyarylene sulfides with alkenyl
aromatic compounds or with vinyl aromatic compounds, and
combinations comprising at least one of the foregoing polyarylene
sulfides. Polyarylene sulfides are known polymers comprising a
plurality of structural units of the formula --R--S-- wherein R is
an aromatic radical such as phenylene, biphenylene, naphthylene,
oxydiphenyl, or diphenyl sulfone. Known methods of preparing
polyarylene sulfides include those described in U.S. Pat. No.
4,490,522 to Kawabata et al and U.S. Pat. No. 4,837,301 to Glock et
al.
[0083] In one aspect, the polyarylene sulfide comprises a plurality
of structural units of the formula:
##STR00001##
wherein for each structural unit, each Q.sup.1 and each Q.sup.2 is
independently hydrogen, halogen, primary or secondary lower alkyl,
phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or
halohydrocarbonoxy wherein at least two carbon atoms separate the
halogen and oxygen atoms. In a further aspect, each Q.sup.1 is
hydrogen, alkyl, or phenyl. In a further aspect, at least one
Q.sup.1 is C.sub.1-4 alkyl. In a further aspect, each Q.sup.2 is
hydrogen.
[0084] In a further aspect, the polyarylene sulfide comprises a
plurality of structural units of the formula:
##STR00002##
wherein for each structural unit, each Q.sup.1 and each Q.sup.2 is
independently hydrogen, halogen, primary or secondary lower alkyl,
phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or
halohydrocarbonoxy wherein at least two carbon atoms separate the
halogen and oxygen atoms. In a further aspect, each Q.sup.1 is
hydrogen, alkyl, or phenyl. In a further aspect, at least one
Q.sup.1 is C.sub.1-4 alkyl. In a further aspect, each Q.sup.2 is
hydrogen.
[0085] PPS is typically prepared by the reaction of
p-dichlorobenzene with sodium sulfide, optionally with the use of a
minor proportion of 1,3,5-trichlorobenzene as a branching agent.
Reference is made, for example, to U.S. Pat. No. 4,794,163, for a
disclosure of typical reagents and conditions employed in
polyarylene sulfide preparation.
[0086] It is often impracticable to determine the molecular weight
of a polyarylene sulfide, by reason of its insolubility in
essentially all solvents used for molecular weight determination.
Indirect characterization of relative molecular weight by melt flow
characteristics is commonly employed. The melt flow characteristics
of the polyarylene sulfides used according to this invention are
not critical; values in the range of 20-1000 g/10 minute
(determined at 315.degree. C. under a 5 kg load) are typical.
[0087] In various aspects, the polyarylene sulfide is polyphenylene
sulfide with a melting temperature of about 270.degree. C. to about
290.degree. C. when determined in accordance with ISO 11357 at
10.degree. C./min and a glass transition temperature of about
80.degree. C. to about 100.degree. C. when determined in accordance
with ISO 11357 at 10.degree. C./min. In a still further aspect, the
polyarylene sulfide is polyphenylene sulfide with a melting
temperature of about 280.degree. C. when determined in accordance
with ISO 11357 at 10.degree. C./min and a glass transition
temperature of about 90.degree. C. when determined in accordance
with ISO 11357 at 10.degree. C./min.
[0088] In various further aspects, the polyarylene sulfide is
polyphenylene sulfide with a melting temperature of about
270.degree. C. to about 290.degree. C. when determined in
accordance with ISO 11357 at 10.degree. C./min; a glass transition
temperature of about 80.degree. C. to about 100.degree. C. when
determined in accordance with ISO 11357 at 10.degree. C./min; a
deflection temperature under load (DTUL) of about 110.degree. C. to
about 120.degree. C. under a load of 1.8 MPa when determined in
accordance with ISO 75; and a deflection temperature under load
(DTUL) of about 90.degree. C. to about 100.degree. C. under a load
of 8.0 MPa when determined in accordance with ISO 75. In a still
further aspect, the polyarylene sulfide is polyphenylene sulfide
with a melting temperature of about 280.degree. C. when determined
in accordance with ISO 11357 at 10.degree. C./min; a glass
transition temperature of about 90.degree. C. when determined in
accordance with ISO 11357 at 10.degree. C./min; a deflection
temperature under load (DTUL) of about 115.degree. C. under a load
of 1.8 MPa when determined in accordance with ISO 75; and a
deflection temperature under load (DTUL) of about 95.degree. C.
under a load of 8.0 MPa when determined in accordance with ISO
75.
D. POLYAMIDES
[0089] In one aspect, the disclosed blended polymer compositions
with improved heat resistance of the present invention comprise an
organic polymer. In one aspect, organic polymers can be polyamide
polymers.
[0090] Polyamides are generally derived from the polymerization of
organic lactams having from 4 to 12 carbon atoms. In various
aspects, the polyamides of the present invention are polymerized
from lactams of the formula:
##STR00003##
wherein n is about 3 to about 11. In a further aspect, the lactam
is epsilon-caprolactam having n equal to 5.
[0091] In various further aspects, the polyamide can be synthesized
using an .alpha.,.beta.-unsaturated gamma-lactone (such as
2(5H-furanone) to effect the regular, sequential alignment of side
chains along a polyamide backbone of the formula:
##STR00004##
wherein n is about 50 to about 10,000, wherein each R is 1 to about
50 carbon atoms and is optionally substituted with heteroatoms,
oxygen, nitrogen, sulfur, or phosphorus and combinations thereof.
Depending on the side group (R), the method can produce many
different types of polyamides. For instance, when R is a saturated
long-chain alkyl group (such as when the amine is tetradecylamine),
a polymer having alkyl chains on one side of the polymer backbone
and hydroxymethyl groups on the other side of the backbone is
formed. When the R group is a polyamine (such as
pentaethylenehexamine), a polymer having amino substituted alkyl
chains on one side of the polymer backbone and hydroxymethyl groups
on the other side of the backbone is formed.
[0092] Polyamides of the present invention can also be synthesized
from amino acids having about 4 to about 12 carbon atoms. In
various aspects, the polyamides of the present invention are
polymerized from amino acids of the formula:
##STR00005##
wherein n is about 3 to about 11. In a further aspect, the amino
acid is epsilon-aminocaproic acid with n equal to about 5.
[0093] Polyamides can also be polymerized from aliphatic
dicarboxylic acids having from about 4 to about 12 carbon atoms and
aliphatic diamines having from about 2 to about 12 carbon atoms. In
various aspects, the polyamides of the present invention are
polymerized from aliphatic diamines of the formula:
H.sub.2N--(CH.sub.2).sub.n--NH.sub.2,
wherein n is about 2 to about 12. In a further aspect, the
aliphatic diamine is hexamethylenediamine
(H.sub.2N(CH.sub.2).sub.6NH.sub.2). In a still further aspect, the
molar ratio of the dicarboxylic acid to the diamine is about 0.66
to about 1.5. In a yet further aspect, the molar ratio is about
0.81 to about 1.22. In an even further aspect, the molar ratio is
about 0.96 to about 1.04.
[0094] The dicarboxylic acids can be aliphatic dicarboxylic acids,
cycloaliphatic dicarboxylic acids, or aromatic dicarboxylic acids.
Examples of aliphatic dicarboxylic acids are aliphatic diacids that
include carboxylic acids having two carboxyl groups. Suitable
examples of cycloaliphatic acids include decahydro naphthalene
dicarboxylic acid, norbornene dicarboxylic acids, bicyclo octane
dicarboxylic acid, cis-1,4-cyclohexanedicarboxylic acid and
trans-1,4-cyclohexanedicarboxylic acids or the like, or a
combination comprising at least one of the foregoing acids. In
various further aspect, cycloaliphatic diacids are
cis-1,4-cyclohexanedicarboxylic acid and
trans-1,4-cyclohexanedicarboxylic acids. Examples of linear
aliphatic diacids are oxalic acid, malonic acid, pimelic acid,
gluteric acid, suberic acid, succinic acid, adipic acid, dimethyl
succinic acid, azelaic acid, or the like, or a combination
comprising at least one of the foregoing acids. Examples of
aromatic dicarboxylic acids are terephthalic acid, phthalic acid,
isophthalic acid, naphthalene dicarboxylic acid, or the like, or a
combination comprising at least one of the foregoing dicarboxylic
acids.
[0095] In various aspects, the polyamides of the present invention
comprise polypyrrolidone (nylon-4), polycaprolactam (nylon-6),
polycapryllactam (nylon-8), polyhexamethylene adipamide
(nylon-6,6), polyundecanolactam (nylon-11), polydodecanolactam
(nylon-12), polyhexamethylene azelaiamide (nylon-6,9),
polyhexamethylene, sebacamide (nylon-6,10), polyhexamethylene
isophthalamide (nylon-6,I), polyhexamethylene terephthalamide
(nylon-6,T), polyamides of hexamethylene diamine and
n-dodecanedioic acid (nylon-6,12), as well as polyamides resulting
from terephthalic acid and/or isophthalic acid and trimethyl
hexamethylene diamine, polyamides resulting from adipic acid and
meta xylenediamines, polyamides resulting from adipic acid, azelaic
acid and 2,2-bis-(p-aminocyclohexyl)propane, polyamides resulting
from terephthalic acid and 4,4'-diamino-dicyclohexylmethane, and
combinations comprising one or more of the foregoing polyamides.
The composition may comprise two or more polyamides. For example
the polyamide may comprise nylon-6 and nylon-6,6.
[0096] Copolymers of the foregoing polyamides are also suitable for
use in the practice of the present disclosure. Exemplary polyamide
copolymers comprise copolymers of hexamethylene
adipamide/caprolactam (nylon-6,6/6), copolymers of
caproamide/undecamide (nylon-6/11), copolymers of
caproamide/dodecamide (nylon-6/12), copolymers of hexamethylene
adipamide/hexamethylene isophthalamide (nylon-6,6/6,I), copolymers
of hexamethylene adipamide/hexamethylene terephthalamide
(nylon-6,6/6,T), copolymers of hexamethylene
adipamide/hexamethylene azelaiamide (nylon-6,6/6,9), and
combinations thereof.
[0097] Polyamides, as used herein, also comprise the toughened or
super tough polyamides. Generally, these super tough nylons are
prepared by blending one or more polyamide with one or more
polymeric or copolymeric elastomeric toughening agent. Suitable
toughening agents can be straight chain or branched as well as
graft polymers and copolymers, including core-shell graft
copolymers, and are characterized as having incorporated therein
either by copolymerization or by grafting on the preformed polymer,
a monomer having functional and/or active or highly polar groupings
capable of interacting with or adhering to the polyamide matrix so
as to enhance the toughness of the polyamide polymer. Super tough
polyamides, or super tough nylons, as they are more commonly known,
include those available commercially, e.g. from E.I. duPont under
the trade name ZYTEL ST, or those prepared in accordance with U.S.
Pat. No. 4,174,358 to Epstein; U.S. Pat. No. 4,474,927 to Novak;
U.S. Pat. No. 4,346,194 to Roura; and U.S. Pat. No. 4,251,644 to
Jeffrion, among others and combinations comprising at least one of
the foregoing, can be employed.
E. POLYOLEFINS
[0098] In one aspect, the disclosed blended polymer compositions
with improved heat resistance of the present invention comprise an
organic polymer. In one aspect, organic polymers can be polyolefin
polymers.
[0099] Polyolefin, as used herein, refers to a class or group name
for thermoplastic polymers derived from simple olefins, including
homo or copolymers of olefins. It is to be understood that
polyolefins are of the general structure: C.sub.nH.sub.2n and
include, but are not limited to, polymers such as, for example,
polyethylene, polypropylene and polyisobutylene. Polyolefin resins
of this general structure and methods for their preparation are
well known in the art and are described for example in U.S. Pat.
Nos. 2,933,480, 3,093,621, 3,211,709, 3,646,168, 3,790,519,
3,884,993, 3,894,999, 4,059,654, 4,166,055 and 4,584,334.
[0100] In various aspects, the polyolefin polymer of the present
invention is selected from a crystalline polypropylene, crystalline
propylene-ethylene block or random copolymer, low density
polyethylene, high density polyethylene, linear low density
polyethylene, ultra-high molecular weight polyethylene,
ethylene-propylene random copolymer, ethylene-propylene-diene
copolymer, and the like. Among such polyolefin resins, exemplary
embodiments include crystalline polypropylene, crystalline
propylene-ethylene copolymer, low-density polyethylene,
high-density polyethylene, linear low-density polyethylene, and
ultra-high molecular weight polyethylene.
[0101] In a further aspect, the polyolefin is selected from
polyethylene, high density polyethylene (HDPE), medium density
polyethylene (MDPE), and isotactic polypropylene. Polyolefins
further include olefin copolymers. Such copolymers include
copolymers of ethylene and alpha olefins like 1-octene, propylene
and 4-methyl-1-pentene as well as copolymers of ethylene and one or
more rubbers and copolymers of propylene and one or more rubbers.
Copolymers of ethylene and C3-C10 monoolefins and non-conjugated
dienes, herein referred to as EPDM copolymers, are also suitable.
Examples of suitable C3-C10 monoolefins for EPDM copolymers include
propylene, 1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene,
2-hexene, 3-hexene, and the like. Suitable dienes include
1,4-hexadiene and monocylic and polycyclic dienes. Mole ratios of
ethylene to other C3-C10 monoolefin monomers can range from 95:5 to
5:95 with diene units being present in the amount of from 0.1 to 10
mole percent. EPDM copolymers can be functionalized with an acyl
group or electrophilic group for grafting onto the polyphenylene
ether as disclosed in U.S. Pat. No. 5,258,455 to Laughner et al.
Olefin copolymers further include linear low density polyethylene
(LLDPE). Total polyolefin further includes the polyolefin segments
of block copolymers, such as the poly(ethylene-butylene) segment of
a polystyrene-poly(ethylene-butylene)-polystyrene block copolymer,
and the poly(ethylene-propylene) segment of a
polystyrene-poly(ethylene-propylene) diblock copolymer.
[0102] In a further aspect, the total polyolefin is selected from
ethylene-octene copolymers, ethylene-butene copolymers,
ethylene-propylene copolymers, polypropylenes, polybutenes, the
poly(ethylene-propylene) blocks of
polystyrene-poly(ethylene-propylene)-polystyrene triblock
copolymers, the poly(ethylene-butylene) blocks of
polystyrene-poly(ethylene-butylene)-polystyrene triblock
copolymers, and mixtures thereof. In a still further aspect, the
polyolefin is selected from polypropylene, polybutene, the
poly(ethylene-propylene) blocks of
polystyrene-poly(ethylene-propylene)-polystyrene triblock
copolymers, the poly(ethylene-butylene) blocks of
polystyrene-poly(ethylene-butylene)-polystyrene triblock
copolymers, and mixtures thereof.
F. POLYESTERS
[0103] In one aspect, the disclosed blended polymer compositions
with improved heat resistance of the present invention comprise an
organic polymer. In one aspect, organic polymers can be polyester
polymers.
[0104] Polyesters are generally polymers in which the backbones are
formed by the esterification condensation of polyfunctional
alcohols and acids. In various aspects, the blended polymer
compositions comprise a polyester polymer, wherein the polyester
polymer is a thermoplastic polyester obtained by polymerizing
bifunctional carboxylic acid and diol monomer units. Aromatic
dicarboxylic acids, for example, terephthalic acid, isophthalic
acid, naphthalene dicarboxylic acid and the like, can be used as
these bifunctional carboxylic acids, and mixtures of these can be
used as needed. Among these, terephthalic acid is particularly
preferred from the standpoint of cost. Also, to the extent that the
effects of this invention are not lost, other bifunctional
carboxylic acids such as aliphatic dicarboxylic acids such as
oxalic acid, malonic acid, adipic acid, suberic acid, azelaic acid,
sebacic acid, decane dicarboxylic acid, and cyclohexane
dicarboxylic acid; and their ester-modified derivatives can also be
used.
[0105] In one aspect, the polyester of the present invention is a
crystalline or amorphous polyesters having repeating structural
units represented by the formula:
##STR00006##
wherein each T is independently a divalent C2-20 aliphatic group,
C5-20 cycloaliphatic group, or C6-20 aromatic group derived from a
dicarboxylic acid or a chemical equivalent thereof; and each D is
independently a divalent C2-20 alkylene group, C6-20 alicyclic
group, C6-20 aromatic group, or poly(C2-6 oxyalkylene) group
derived from a dihydroxy compound or a chemical equivalent thereof.
Copolyesters containing a combination of different T and/or D
groups can be used. Chemical equivalents of diacids include the
corresponding esters, alkyl esters, e.g., C1-3 dialkyl esters,
diaryl esters, anhydrides, salts, acid chlorides, acid bromides,
and the like. Chemical equivalents of dihydroxy compounds include
the corresponding esters, such as C1-3 dialkyl esters, diaryl
esters, and the like. The polyesters can be branched or linear.
[0106] In a further aspect, a C6-C20 aromatic carboxylic acid
monomer can be used as the dicarboxylic acid. In a still further
aspect, the C6-20 aromatic dicarboxylic acid is selected from
isophthalic acid, terephthalic acid, 1,2-di(p-carboxyphenyl)ethane,
4,4'-dicarboxydiphenyl ether, 4,4'-bisbenzoic acid, and the like,
and 1,4- or 1,5-naphthalene dicarboxylic acids and the like. In
various aspects, a combination of isophthalic acid and terephthalic
acid can be used, wherein the weight ratio of isophthalic acid to
terephthalic acid is 91:9 to 2:98, specifically 25:75 to 2:98.
[0107] In a further aspect, a C5-20 cycloaliphatic dicarboxylic
acids comprising at least one cycloaliphatic moiety is the
dicarboxylic acid monomer used to prepare the polyester of the
present invention. In a still further aspect, the C5-20
cycloaliphatic dicarboxylic acid comprise at least one
cycloaliphatic moiety and is selected from monocyclo- and
bicyclo-aliphatic acids such as decahydronaphthalene dicarboxylic
acids, norbornene dicarboxylic acids, bicyclooctane dicarboxylic
acids, 1,4-cyclohexanedicarboxylic acid (both cis and trans),
specifically trans-1,4-cyclohexanedicarboxylic acid,
1,4-hexylenedicarboxylic acid, and the like. Aliphatic C2-20
dicarboxylic acids such as adipic acid, azelaic acid, dicarboxyl
dodecanoic acid, and succinic acid can also be useful.
[0108] In a further aspect, the diol monomer used to prepare the
polyester can be a straight chain aliphatic and cycloaliphatic
diols having 2 to 15 carbon atoms. In a still further aspect, the
diol is selected from ethylene glycol, propylene glycol,
1,4-butanediol, trimethylene glycol, tetramethylene glycol,
neopentyl glycol, diethylene glycol, cyclohexane dimethanol,
heptane-1,7-diol, octane-1,8-diol, neopentyl glycol,
decane-1,10-diol, etc.; polyethylene glycol; bivalent phenols such
as dihydroxydiarylalkanes such as 2,2-bis(4-hydroxylphenyl)propane
that can be called bisphenol-A, bis(4-hydroxyphenyl) methane,
bis(4-hydroxyphenyl)naphthylmethane,
bis(4-hydroxyphenyl)phenylmethane,
bis(4-hydroxyphenyl)-(4-isopropylphenyl)methane,
bis(3,5-dichloro-4-hydroxyphenyl)methane,
bis(3,5-dimethyl-4-hydroxyphenyl)methane,
1,1-bis(4-hydroxyphenyl)ethane,
1-naphthyl-1,1-bis(4-hydroxyphenyl)ethane,
1-phenyl-1,1-bis(4-hydroxyphenyl)ethane,
1,2-bis(4-hydroxyphenyl)ethane,
2-methyl-1,1-bis(4-hydroxyphenyl)propane,
2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane,
1-ethyl-1,1-bis(4-hydroxyphenyl)propane,
2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane,
2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane,
2,2-bis(3-chloro-4-hydroxyphenyl)propane,
2,2-bis(3-methyl-4-hydroxyphenyl)propane,
2,2-bis(3-fluoro-4-hydroxyphenyl)propane,
1,1-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)butane,
1,4-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane,
4-methyl-2,2-bis(4-hydroxyphenyl)pentane,
2,2-bis(4-hydroxyphenyl)hexane, 4,4-bis(4-hydroxyphenyl)heptane,
2,2-bis(4-hydroxyphenyl)nonane, 1,10-bis(4-hydroxyphenyl)decane,
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and
2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane;
dihyroxydiarylcycloalkanes such as
1,1-bis(4-hydroxyphenyl)cyclohexane,
1,1-bis(3,5-dichloro-4-hydroxyphenyl)cyclohexane, and
1,1-bis(4-hydroxyphenyl)cyclodecane; dihydroxydiarylsulfones such
as bis(4-hydroxyphenyl)sulfone, and
bis(3,5-dimethyl-4-hydroxyphenyl)sulfone,
bis(3-chloro-4-hydroxyphenyl)sulfone; dihydroxydiarylethers such as
bis(4-hydroxyphenyl)ether, and
bis(3-5-dimethyl-4-hydroxyphenyl)ether; dihydroxydiaryl ketones
such as 4,4'-dihydroxybenzophenone, and
3,3',5,5'-tetramethyl-4,4-diydroxybenzophenone; dihydroxydiaryl
sulfides such as bis(4-hydroxyphenyl)sulfide,
bis(3-methyl-4-hydroxyphenyl)sulfide, and
bis(3,5-dimethyl-4-hydroxyphenyl)sulfide; dihydroxydiaryl
sulfoxides such as bis(4-hydroxyphenyl)sulfoxide;
dihydroxydiphenyls such as 4,4'-dihydroxyphenyl;
dihydroxyarylfluorenes such as 9,9-bis(4-hydroxyphenyl)fluorene;
dihydroxybenzenes such as hydroxyquinone, resorcinol, and
methylhydroxyquinone; and dihydroxynaphthalenes such as
1,5-dihydroxynaphthalene and 2,6-dihydroxynaphthalene. Also, two or
more kinds of diols can be combined as needed.
[0109] In a further aspect, the diol monomer used to prepare the
polyester is an aliphatic diol. In a still further aspect, the
aliphatic diol is selected from ethylene glycol, 1,2-propylene
glycol, 1,3-propylene glycol, 2,2-dimethyl-1,3-propane diol,
2-ethyl-2-methyl-1,3-propane diol, 1,4-butane diol, 1,4-but-2-ene
diol, 1,3-1,5-pentane diol, 1,5-pentane diol, dipropylene glycol,
2-methyl-1,5-pentane diol, and the like. In a still further aspect,
the diol monomer is a diol comprising a cyloaliphatic moiety. In a
yet further aspect, the diol comprising a cyloaliphatic moiety is
selected from 1,6-hexane diol, dimethanol decalin, dimethanol
bicyclooctane, 1,4-cyclohexane dimethanol (including its cis- and
trans-isomers), triethylene glycol, 1,10-decanediol, and the like.
Chemical equivalents of the diols include esters, such as C1-3
dialkyl esters, diaryl esters, and the like.
[0110] In a further aspect, the polyester of the present invention
is selected from polyethylene terephthalate, polybutylene
terephthalate, polyethylene naphthalate, polybutylene naphthalate,
polytrimethylene terephthalate, poly(1,4-cyclohexylenedimethylene
1,4-cyclohexanedicarboxylate), poly(1,4-cyclohexylenedimethylene
terephthalate), poly(cyclohexylenedimethylene-co-ethylene
terephthalate), or a combination comprising at least one of the
foregoing polyesters. In a still further aspect, the polyester of
the present invention is selected from polyethylene terephthalate
(PET) and polybutylene terephthalate (PBT).
[0111] In a further aspect, the polyester of the present invention
is selected from poly(alkylene terephthalate)polyesters include
poly(ethylene terephthalate) (PET), poly(butylene terephthalate)
(PBT), poly(ethylene naphthalate) (PEN), poly(butylene naphthalate)
(PBN), and poly(1,3-propylene terephthalate) (PPT).
[0112] In various further aspects, the polyester of the present
invention is selected from poly(1,4-cyclohexylenedimethylene
terephthalate) (PCT), poly(1,4-cyclohexylenedimethylene
cyclohexane-1,4-dicarboxylate) also known as
poly(cyclohexane-14-dimethanol cyclohexane-1,4-dicarboxylate)
(PCCD), and poly(1,4-cyclohexylenedimethylene
terephthalate-co-isophthalate) (PCTA).
[0113] In a further aspect, the polyester of the present invention
is a copolyester derived from an aromatic dicarboxylic acid
(specifically terephthalic acid and/or isophthalic acid) and a
mixture comprising a linear C2-6 aliphatic diol (specifically
ethylene glycol and butylene glycol); and a C6-12 cycloaliphatic
diol (specifically 1,4-hexane diol, dimethanol decalin, dimethanol
bicyclooctane, 1,4-cyclohexane dimethanol and its cis- and
trans-isomers, 1,10-decane diol, and the like) or a linear
poly(C2-6 oxyalkylene)diol (specifically, poly(oxyethylene)glycol)
and poly(oxytetramethylene)glycol). The poly(oxyalkylene)glycol can
have a molecular weight of 200 to 10,000 grams per mole, more
specifically 400 to 6,000 grams per mole, even more specifically
600 to 2,000 grams per mole, and a carbon to oxygen ratio of 1 to
10, more specifically 1.5 to 6, even more specifically 2.0 to 4.3.
The ester units comprising the two or more types of diols can be
present in the polymer chain as individual units or as blocks of
the same type of units.
[0114] In a further aspect, the copolyester is selected from
poly(1,4-cyclohexylene dimethylene co-ethylene terephthalate)
(PCTG) wherein greater than 50 mol % of the ester groups are
derived from 1,4-cyclohexanedimethanol; and
poly(ethylene-co-1,4-cyclohexylenedimethylene terephthalate)
wherein greater than 50 mol % of the ester groups are derived from
ethylene (PTCG). Also included are thermoplastic poly(ester-ether)
(TPEE) copolymers such as poly(ethylene-co-poly(oxytetramethylene)
terephthalate. Also contemplated for use herein are any of the
above polyesters with minor amounts, e.g., from 0.5 to 5 percent by
weight, of units derived from aliphatic acid and/or aliphatic
polyols to form copolyesters. The aliphatic polyols include
glycols, such as poly(ethylene glycol) or poly(butylene glycol).
Such polyesters can be made following the teachings of, for
example, U.S. Pat. Nos. 2,465,319 and 3,047,539.
[0115] The polyesters can be obtained by methods well known to
those skilled in the art, including, for example, interfacial
polymerization, melt-process condensation, solution phase
condensation, and transesterification polymerization. Such
polyester resins are typically obtained by the condensation or
ester interchange polymerization of the diacid or diacid chemical
equivalent component with the diol or diol chemical equivalent
component with the component. The condensation reaction may be
facilitated by the use of a catalyst of the type known in the art,
with the choice of catalyst being determined by the nature of the
reactants. For example, a dialkyl ester such as dimethyl
terephthalate can be transesterified with butylene glycol using
acid catalysis, to generate poly(butylene terephthalate). As can be
appreciated by one skilled in the art, polyesters can be produced
in the presence or absence of common polymerization catalysts
represented by titanium, germanium, antimony or the like; and can
be produced by interfacial polymerization, melt polymerization or
the like.
[0116] In various aspects, the polyester polymer of the present
invention can be a single kind of thermoplastic polyester used
alone, or two or more kinds used in combination. Furthermore,
copolyesters can also be used as needed. In a further aspect, a
polyester comprising two or more kinds of polyesters in combination
is a combination of polybutylene terephthalate and polyethylene
terephthalate, or the like.
G. THERMALLY CONDUCTIVE ADDITIVE
[0117] The inventive composition comprises a thermally conductive
additive such as a inorganic filler material. In various aspects,
the thermally conductive additive can comprise magnesium hydroxide
(Mg(OH).sub.2) or an aluminum oxide hydroxide. In one aspect, the
thermally conductive additive comprises magnesium hydroxide. In
another aspect, the thermally conductive additive comprises
aluminum oxide hydroxide. In various further aspects, the thermally
conductive additive is selected from alumina, aluminum oxide,
aluminum trihydroxide and magnesium hydroxide.
[0118] In a further aspect, the thermally conductive additive has a
thermal conductivity of at least about 5.0 W/mK. In a still further
aspect, the thermally conductive additive has a thermal
conductivity of at least about 6.0 W/mK. In a yet further aspect,
the thermally conductive additive has a thermal conductivity of at
least about 7.0 W/mK. In an even further aspect, the thermally
conductive additive has a thermal conductivity of at least about
8.0 W/mK. In a still further aspect, the thermally conductive
additive has a thermal conductivity of at least about 9.0 W/mK. In
a yet further aspect, the thermally conductive additive has a
thermal conductivity of at least about 10.0 W/mK.
[0119] In various further aspects, the thermally conductive
additive is selected from alumina, aluminum oxide
(Al.sub.2O.sub.3), aluminum trihydroxide, magnesium hydroxide,
beryllium oxide, magnesium oxide, zinc oxide, boron nitride,
aluminum nitride and silicon carbide.
[0120] In a further aspect, the thermally conductive additive is
magnesium hydroxide without surface treatment. Suitable forms of
magnesium hydroxide are commercially available, and include, for
example, MAGNIFIN H5 IV from Martinswerk GmbH (Bergheim, Germany).
In a still further aspect, the thermally conductive additive is
magnesium hydroxide that has been pre-treated with a vinyl silane.
Such silane-treated magnesium hydroxide is commercially available,
for example, as MAGNIFIN H5A and MAGNIFIN H5MV from Martinswerk
GmbH (Bergheim, Germany).
[0121] In a further aspect, the magnesium hydroxide is particulate.
The particulate magnesium hydroxide can be a finely divided solid
material have a particle size, d.sub.10, from about 0.5 to about
1.5 .mu.m. In a still further aspect, the magnesium hydroxide has a
particle size, d.sub.10, from about 0.6 to about 1.2 .mu.m. In a
yet further aspect, the magnesium hydroxide has a particle size,
d.sub.10, from about 0.7 to about 1.0 .mu.m. In a still further
aspect, the magnesium hydroxide has a particle size, d.sub.90, from
about 2.0 to about 5.0 .mu.m. In a yet further aspect, the
magnesium hydroxide has a particle size, d.sub.90, from about 2.2
to about 4.8 .mu.m. In an even further aspect, the magnesium
hydroxide has a particle size, d.sub.90, from about 2.4 to about
4.4 .mu.m.
[0122] The concentration of the thermally conductive additive can
vary, and the present invention is not intended to be limited to
any particular thermally conductive additive concentration. In one
aspect, the inventive composition comprises from about 30 wt % to
about 70 wt % of thermally conductive additive, for example, about
30, 35, 40, 45, 50, 55, 60 or 70 wt %. In a further aspect, the
inventive composition comprises about 35 wt % to about 65 wt % of a
thermally conductive additive. In a still further aspect, the
inventive composition comprises about 40 wt % to about 60 wt % of a
thermally conductive additive. In a yet further aspect, the
inventive composition comprises about 45 wt % to about 55 wt % of a
thermally conductive additive. In an even further aspect, the
inventive composition comprises about 47 wt % to about 57 wt % of a
thermally conductive additive. In a still further aspect, the
inventive composition comprises about 50 wt % to about 55 wt % of a
thermally conductive additive. In a yet further aspect, the
inventive composition comprises about 47 wt % to about 55 wt % of a
thermally conductive additive.
[0123] In various further aspects, the inventive composition
comprises about 45.0 wt % of a thermally conductive additive. In a
further aspect, the inventive composition comprises about 47.5 wt %
of a thermally conductive additive. In a still further aspect, the
inventive composition comprises about 50 wt % of a thermally
conductive additive. In a yet further aspect, the inventive
composition comprises about 52.5 wt % of a thermally conductive
additive. In an even further aspect, the inventive composition
comprises about 55 wt % of a thermally conductive additive.
[0124] In a further aspect, the inventive composition comprises
about 45.1 wt % of a thermally conductive additive. In a yet
further aspect, the inventive composition comprises about 49 wt %
of a thermally conductive additive. In an even further aspect, the
inventive composition comprises about 52.6 wt % of a thermally
conductive additive.
[0125] In a further aspect, the inventive composition comprises
about 46 wt % of a thermally conductive additive. In a yet further
aspect, the inventive composition comprises about 47 wt % of a
thermally conductive additive. In an even further aspect, the
inventive composition comprises about 48 wt % of a thermally
conductive additive. In a still further aspect, the inventive
composition comprises about 49 wt % of a thermally conductive
additive. In a yet further aspect, the inventive composition
comprises about 50 wt % of a thermally conductive additive. In an
even further aspect, the inventive composition comprises about 51
wt % of a thermally conductive additive. In a still further aspect,
the inventive composition comprises about 53 wt % of a thermally
conductive additive. In a yet further aspect, the inventive
composition comprises about 54 wt % of a thermally conductive
additive. In an even further aspect, the inventive composition
comprises about 56 wt % of a thermally conductive additive. In a
still further aspect, the inventive composition comprises about 57
wt % of a thermally conductive additive.
[0126] In one aspect, the inventive composition comprises from
about 30 wt % to about 70 wt % of Mg(OH).sub.2, for example, about
30, 35, 40, 45, 50, 55, 60 or 70 wt %. In a further aspect, the
inventive composition comprises about 35 wt % to about 65 wt % of
Mg(OH).sub.2. In a still further aspect, the inventive composition
comprises about 40 wt % to about 60 wt % of Mg(OH).sub.2. In a yet
further aspect, the inventive composition comprises about 45 wt %
to about 55 wt % of Mg(OH).sub.2. In an even further aspect, the
inventive composition comprises about 47 wt % to about 57 wt % of a
Mg(OH).sub.2. In a still further aspect, the inventive composition
comprises about 50 wt % to about 55 wt % of Mg(OH).sub.2. In a yet
further aspect, the inventive composition comprises about 47 wt %
to about 55 wt % of Mg(OH).sub.2.
[0127] In various further aspects, the inventive composition
comprises about 45.0 wt % of Mg(OH).sub.2. In a further aspect, the
inventive composition comprises about 47.5 wt % of Mg(OH).sub.2. In
a still further aspect, the inventive composition comprises about
50 wt % of Mg(OH).sub.2. In a yet further aspect, the inventive
composition comprises about 52.5 wt % of Mg(OH).sub.2. In an even
further aspect, the inventive composition comprises about 55 wt %
of Mg(OH).sub.2.
[0128] In a further aspect, the inventive composition comprises
about 45.1 wt % of Mg(OH).sub.2. In a yet further aspect, the
inventive composition comprises about 49 wt % of Mg(OH).sub.2. In
an even further aspect, the inventive composition comprises about
52.6 wt % of Mg(OH).sub.2.
[0129] In a further aspect, the inventive composition comprises
about 46 wt % of Mg(OH).sub.2. In a yet further aspect, the
inventive composition comprises about 47 wt % of Mg(OH).sub.2. In
an even further aspect, the inventive composition comprises about
48 wt % of Mg(OH).sub.2. In a still further aspect, the inventive
composition comprises about 49 wt % of Mg(OH).sub.2. In a yet
further aspect, the inventive composition comprises about 50 wt %
of Mg(OH).sub.2. In an even further aspect, the inventive
composition comprises about 51 wt % of Mg(OH).sub.2. In a still
further aspect, the inventive composition comprises about 53 wt %
of Mg(OH).sub.2. In a yet further aspect, the inventive composition
comprises about 54 wt % of Mg(OH).sub.2. In an even further aspect,
the inventive composition comprises about 56 wt % of Mg(OH).sub.2.
In a still further aspect, the inventive composition comprises
about 57 wt % of Mg(OH).sub.2.
[0130] In one aspect, the inventive composition comprises from
about 30 wt % to about 70 wt % of an aluminum oxide hydroxide, for
example, about 30, 35, 40, 45, 50, 55, 60 or 70 wt %. In a further
aspect, the inventive composition comprises about 35 wt % to about
65 wt % of an aluminum oxide hydroxide. In a still further aspect,
the inventive composition comprises about 40 wt % to about 60 wt %
of an aluminum oxide hydroxide. In a yet further aspect, the
inventive composition comprises about 45 wt % to about 55 wt % of
an aluminum oxide hydroxide. In an even further aspect, the
inventive composition comprises about 47 wt % to about 57 wt % of a
an aluminum oxide hydroxide. In a still further aspect, the
inventive composition comprises about 50 wt % to about 55 wt % of
an aluminum oxide hydroxide. In a yet further aspect, the inventive
composition comprises about 47 wt % to about 55 wt % of an aluminum
oxide hydroxide.
[0131] In various further aspects, the inventive composition
comprises about 45.0 wt % of an aluminum oxide hydroxide. In a
further aspect, the inventive composition comprises about 47.5 wt %
of an aluminum oxide hydroxide. In a still further aspect, the
inventive composition comprises about 50 wt % of an aluminum oxide
hydroxide. In a yet further aspect, the inventive composition
comprises about 52.5 wt % of an aluminum oxide hydroxide. In an
even further aspect, the inventive composition comprises about 55
wt % of an aluminum oxide hydroxide.
[0132] In a further aspect, the inventive composition comprises
about 45.1 wt % of an aluminum oxide hydroxide. In a yet further
aspect, the inventive composition comprises about 49 wt % of an
aluminum oxide hydroxide. In an even further aspect, the inventive
composition comprises about 52.6 wt % of an aluminum oxide
hydroxide.
[0133] In a further aspect, the inventive composition comprises
about 46 wt % of an aluminum oxide hydroxide. In a yet further
aspect, the inventive composition comprises about 47 wt % of an
aluminum oxide hydroxide. In an even further aspect, the inventive
composition comprises about 48 wt % of an aluminum oxide hydroxide.
In a still further aspect, the inventive composition comprises
about 49 wt % of an aluminum oxide hydroxide. In a yet further
aspect, the inventive composition comprises about 50 wt % of an
aluminum oxide hydroxide. In an even further aspect, the inventive
composition comprises about 51 wt % of an aluminum oxide hydroxide.
In a still further aspect, the inventive composition comprises
about 53 wt % of an aluminum oxide hydroxide. In a yet further
aspect, the inventive composition comprises about 54 wt % of an
aluminum oxide hydroxide. In an even further aspect, the inventive
composition comprises about 56 wt % of an aluminum oxide hydroxide.
In a still further aspect, the inventive composition comprises
about 57 wt % of an aluminum oxide hydroxide.
[0134] In various further aspects, an aluminum oxide hydroxide can
be used as the thermally conductive additive. In a still further
aspect, the aluminum oxide hydroxide is selected from boehmite,
pseudo-boehmite .alpha.-aluminum monohydrate, AlO(OH) or
.alpha.-Al2O3.H2O), and diaspore (.beta.-aluminum monohydrate,
AlO(OH) or .beta.-Al2O3.H2O). In a yet further aspect, the aluminum
oxide hydroxide is selected from boehmite and pseudo-boehmite. In
an even further aspect, the aluminum oxide hydroxide is boehmite.
In a still further aspect, the aluminum oxide hydroxide is
pseudo-boehmite.
[0135] In one aspect, the blended polymer compositions of the
present invention further comprise a high thermally conductive
additive. In a further aspect, the high thermally conductive
additive is graphite. In a still further aspect, the high-thermal
conductive filler has a thermal conductivity greater than or equal
to about 10 W/mK. In a yet further aspect, the high-thermal
conductive filler has a thermal conductivity greater than or equal
to about 25 W/mK.
[0136] In a further aspect, the high-thermal conductive filler is
selected from AlN (aluminum nitride), Al.sub.4C.sub.3 (aluminum
carbide), Al.sub.2O.sub.3 (aluminum oxide), BN (Boron nitride),
AlON (aluminum oxynitride), MgSiN.sub.2 (magnesium silicon
nitride), SiC (silicon carbide), Si.sub.3N.sub.4 (Silicon nitride),
graphite, expanded graphite, graphene, and carbon fiber. In a still
further aspect, the high-thermal conductive filler is selected from
graphite, expanded graphite, graphene, and carbon fiber. In a yet
further aspect, the high-thermal conductive filler is a
graphite.
[0137] In one aspect, the inventive composition further comprises
from about 0.1 wt % to about 25 wt % of high thermally conductive
additive, for example, about 0.1, 0.25, 0.5, 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24,
or 25 wt %. In a further aspect, the blended polymer compositions
further comprise about 10 wt % to about 25 wt % of a high thermally
conductive additive. In an even further aspect, the blended polymer
compositions further comprise about 10 wt % to about 20 wt % of a
high thermally conductive additive. In a still further aspect, the
blended polymer compositions further comprise about 11 wt % to
about 19 wt % of a high thermally conductive additive. In a yet
further aspect, the blended polymer compositions further comprise
about 12 wt % to about 18 wt % of a high thermally conductive
additive. In an even further aspect, the blended polymer
compositions further comprise about 13 wt % to about 17 wt % of a
high thermally conductive additive. In a still further aspect, the
blended polymer compositions further comprise about 15 wt % to
about 20 wt % of a high thermally conductive additive. In a yet
further aspect, the blended polymer compositions further comprise
about 16 wt % to about 18 wt % of a high thermally conductive
additive.
[0138] In a further aspect, the blended polymer compositions
further comprise about 10 wt % of a high thermally conductive
additive. In a still further aspect, the blended polymer
compositions further comprise about 11 wt % of a high thermally
conductive additive. In a yet further aspect, the blended polymer
compositions further comprise about 12 wt % of a high thermally
conductive additive. In an even further aspect, the blended polymer
compositions further comprise about 13 wt % of a high thermally
conductive additive. In a still further aspect, the blended polymer
compositions further comprise about 14 wt % of a high thermally
conductive additive. In an even further aspect, the blended polymer
compositions further comprise about 15 wt % of a high thermally
conductive additive. In a still further aspect, the blended polymer
compositions further comprise about 16 wt % of a high thermally
conductive additive. In a yet further aspect, the blended polymer
compositions further comprise about 17 wt % of a high thermally
conductive additive. In a still further aspect, the blended polymer
compositions further comprise about 17.5 wt % of a high thermally
conductive additive. In an even further aspect, the blended polymer
compositions further comprise about 18 wt % of a high thermally
conductive additive. In a still further aspect, the blended polymer
compositions further comprise about 19 wt % of a high thermally
conductive additive. In a yet further aspect, the blended polymer
compositions comprise about 20 wt % of a high thermally conductive
additive.
[0139] In one aspect, the inventive composition further comprises
from about 0.1 wt % to about 25 wt % of graphite, for example,
about 0.1, 0.25, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13,
14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25 wt %. Ina further
aspect, the blended polymer compositions further comprise about 10
wt % to about 20 wt % of graphite. In a still further aspect, the
blended polymer compositions further comprise about 11 wt % to
about 19 wt % of graphite. In a yet further aspect, the blended
polymer compositions further comprise about 12 wt % to about 18 wt
% of graphite. In an even further aspect, the blended polymer
compositions further comprise about 13 wt % to about 17 wt % of
graphite. In a still further aspect, the blended polymer
compositions further comprise about 15 wt % to about 20 wt % of
graphite. In a yet further aspect, the blended polymer compositions
further comprise about 16 wt % to about 18 wt % of graphite.
[0140] In a further aspect, the blended polymer compositions
further comprise about 10 wt % of graphite. In a still further
aspect, the blended polymer compositions further comprise about 11
wt % of graphite. In a yet further aspect, the blended polymer
compositions further comprise about 12 wt % of graphite. In an even
further aspect, the blended polymer compositions further comprise
about 13 wt % of graphite. In a still further aspect, the blended
polymer compositions further comprise about 14 wt % of graphite. In
an even further aspect, the blended polymer compositions further
comprise about 15 wt % of graphite. In a still further aspect, the
blended polymer compositions further comprise about 16 wt % of
graphite. In a yet further aspect, the blended polymer compositions
further comprise about 17 wt % of graphite. In an even further
aspect, the blended polymer compositions further comprise about 18
wt % of graphite. In a still further aspect, the blended polymer
compositions further comprise about 19 wt % of graphite. In a yet
further aspect, the blended polymer compositions comprise about 20
wt % of graphite.
[0141] In various aspects, the graphite is selected from
graphitized carbon fiber, natural graphite, synthetic graphite, and
spherical graphite particles. The graphite used in the present
invention can be synthetically produced or naturally produced, or
can be expandable graphite or expanded graphite with a thickness
smaller than 1 micron. In one aspect, the graphite is naturally
produced. There are three types of naturally produced graphite that
are commercially available. They are flake graphite, amorphous
graphite and crystal vein graphite. In one aspect, the graphite is
flake graphite, wherein the flake graphite is typically found as
discrete flakes ranging in size from 10-800 micrometers in diameter
and 1-150 micrometers thick and purities ranging from 80-99.9%
carbon. In another aspect the graphite is spherical.
[0142] In various further aspects, the blended polymer compositions
of the present invention further comprise a graphite or carbon
black as second thermally conductive additive. In a further aspect,
the blended polymer compositions comprise a graphite. In addition,
while the compositions of the present invention are described as
being further comprising a graphite or a carbon black, it is to be
understood that other crystalline or amorphous carbon materials
such as vitreous carbon, activated charcoal, activated carbon,
carbon fiber or the like may be used in alternative embodiments.
The other crystalline or amorphous carbon materials may, in one
embodiment, be used in lieu of the carbon black or, in an
alternative embodiment, may be used in conjunction with the carbon
black and the graphite.
H. COMPATIBILIZING AGENT
[0143] The inventive blended polymer compositions can further
comprise a compatibilizing agent to improve the physical properties
of the blend, as well as to enable the use of a greater proportion
of the organic polymer component, e.g. the polyamide component.
When used herein, the expression "compatibilizing agent" refers to
those polyfunctional compounds which interact with the char-forming
polymer (e.g. a polyarylene sulfide), the organic polymer component
(e.g. a polyamide), or, preferably, both. This interaction can be
chemical (e.g. grafting) or physical (e.g. affecting the surface
characteristics of the dispersed phases). However, in either case
the resulting blend exhibits improved compatibility, particularly
as evidenced by enhanced impact strength, mold knit line strength
and/or elongation. As used herein, the expression "compatibilized
blended polymer composition" refers to those compositions which
have been physically or chemically compatibilized with an agent as
discussed herein.
[0144] Suitable compatibilizing agents include, for example, liquid
diene polymers, epoxy compounds, oxidized polyolefin wax, quinones,
organosilane compounds, polyfunctional compounds, and
functionalized polyphenylene ethers obtained by reacting one or
more of the previously mentioned compatibilizing agents with
polyphenylene ether. The above and other compatibilizing agents are
more fully described in U.S. Pat. Nos. 4,315,086; 4,600,741;
4,642,358; 4,826,933; 4,866,14; 4,927,894; 4,980,424; 5,041,504;
and 5,115,042. The foregoing compatibilizing agents may be used
alone or in various combinations of one another with another.
Furthermore, they may be added directly to the melt blend or
pre-reacted with either or both the polyphenylene ether and
polyamide, as well as with other resinous materials employed in the
preparation of the compositions of the present invention.
[0145] In a further aspect, the inventive blended polymer
composition comprises a compatibilizing agent, such as, for
example, a dime acid diglycidyl ester epoxy (DADGE.RTM., available
from Aldrich), a 3,4-epoxy cyclohexyl methyl-3,4-epoxy cyclohexane
carboxylate (ERL-4221, available from Aldrich), a modified styrene
acrylic polymer (ADR-4368C, available from multiple sources,
including BASF), or a combination thereof. In other aspects, the
inventive polymer composition can comprise a compatibilizing agent
not specifically recited herein, provided that such a
compatibilizing agent is chemically compatible with the remaining
components of the composition and that the compatibilizing agent
does not adversely affect the desired properties of the
composition. In one aspect, the inventive blended polymer
compositions comprise DADGE. In another aspect, the inventive
blended polymer compositions comprise ERL-4221. In yet another
aspect, the inventive blended polymer compositions comprise
ADR-4368C. In another aspect, the inventive blended polymer
compositions comprise do not comprise a compatibilizing agent.
[0146] In various further aspects, the compatibilizing agent is
anepoxy-functional styrene-acrylate oligomer. One such oligomer
suitable for use in the present invention is marketed by BASF
Corporation as Joncryl.TM. brand chain extender, e.g. JONCRYL.RTM.
ADR-4368-C. Additional information about the epoxy functional low
molecular weight styrene-acrylate copolymer is disclosed in U.S.
Pat. No. 6,605,681 (Villalobos et al.) and U.S. Pat. No. 6,984,694
(Blasius et al), which are incorporated by reference herein.
[0147] In various aspects, the oligomeric chain extender is the
polymerization product of (i) at least one epoxy-functional
(meth)acrylic monomer; and (ii) at least one styrenic and/or
(meth)acrylic monomer, wherein the polymerization product has an
epoxy equivalent weight of from about 180 to about 2800, a
number-average epoxy functionality (Efn) value of less than about
30, a weight-average epoxy functionality (Efw) value of up to about
140, and a number-average molecular weight (Mn) value of less than
6000. In a further aspect, the oligomeric chain extender a
polydispersity index of from about 1.5 to about 5.
[0148] Various Joncryl.TM. grades available and useful from BASF
are ADR-4300, ADR-4370-S, ADR-4368-F, and ADR-4368-C, which are all
solids. Alternatively, one can use liquid grades, namely: ADR-4380,
ADR-4385, and ADR-4318. In a further aspect, the oligomeric chain
extender is Joncryl.TM. ADR-4368-C grade. The number average
molecular weight of this grade is less than 3000 with approximately
4 epoxy functionalities per polymer chain. In a further aspect, the
oligomeric chain extender is an epoxy-functional styrene-acrylate
oligomer having a structure represented by a formula:
##STR00007##
wherein R.sub.1-R.sub.5 can be hydrogen, methyl, a higher alkyl
group having from 2 to 10 carbon atoms, or combinations thereof;
and Re can be an alkyl group; and wherein x, y, and z each can be
between 1 and 20.
[0149] A compatibilizing agent, if present, can be present at any
concentration that can maintain or improve the properties of the
resulting material. The initial amount present will be dependent
upon the specific compatibilizing agent chosen and the specific
polymeric system to which it is added. In various aspects, the
compatibilizing agent can be present in an amount of from about 0.1
wt % to about 5 wt %, for example, about 0.1, 0.3, 0.5, 0.7, 0.9,
1,2, 1.4, 1.6, 1.8, 2, 2.5, 3, 3.5, 4, 4.5, or 5 wt %; or from
about 0.5 wt % to about 1.0 wt %, for example, about 0.5, 0.6, 0.7,
0.8, 0.9, or 1 wt %. In other aspects, the compatibilizing agent
can be present in an amount less than about 0.1 wt % or greater
than about 5 wt %, and the present invention is not intended to be
limited to any particular compatibilizing agent concentration. In
one aspect, when present, the compatibilizing agent can be present
in an amount of about 0.01 weight percent to about 5 wt %, based on
the total weight of the composition. In a further aspect, the
compatibilizing agent is present in an amount from about 0.1 to
about 2 wt %. In a still further aspect, the compatibilizing agent
is present in an amount from about 0.1 to about 0.5 wt %. In one
aspect, a polymer material comprises about 0.25% of a styrenic
epoxy material, such as, for example, ADR-4368C. In another aspect,
a polymer material comprises about 0.5 wt % of a styrenic epoxy
material, such as, for example, ADR-4368-C.
I. REINFORCING FILLERS AND FIBERS
[0150] In other aspects, the inventive polymer composition can
comprise a filler, such as, for example, an inorganic filler. The
specific composition of a filler, if present, can vary, provided
that the filler is chemically compatible with the remaining
components of the polymer composition. In one aspect, the polymer
composition comprises a filler, such as, for example, talc. If
present, the amount of filler can comprise any amount suitable for
a polymer composition that does not adversely affect the desired
properties thereof. In one aspect, the inventive polymer comprises
about 1 wt % to about 25 wt % of a filler.
[0151] In various aspects, the filler is a reinforcing filler. In a
further aspect, the reinforcing filler is a reinforcing fiber.
[0152] In another aspect, a filler can comprise silicates and
silica powders such as aluminum silicate (mullite), synthetic
calcium silicate, zirconium silicate, fused silica, crystalline
silica graphite, natural silica sand, or the like; boron powders
such as boron-nitride powder, boron-silicate powders, or the like;
oxides such as TiO.sub.2, aluminum oxide, magnesium oxide, or the
like; calcium sulfate (as its anhydride, dihydrate or trihydrate);
calcium carbonates such as chalk, limestone, marble, synthetic
precipitated calcium carbonates, or the like; talc, including
fibrous, modular, needle shaped, lamellar talc, or the like;
wollastonite; surface-treated wollastonite; glass spheres such as
hollow and solid glass spheres, silicate spheres, cenospheres,
aluminosilicate (armospheres), or the like; kaolin, including hard
kaolin, soft kaolin, calcined kaolin, kaolin comprising various
coatings known in the art to facilitate compatibility with the
polymeric matrix resin, or the like; single crystal fibers or
"whiskers" such as silicon carbide, alumina, boron carbide, iron,
nickel, copper, or the like; fibers (including continuous and
chopped fibers) such as asbestos, carbon fibers, glass fibers, such
as E, A, C, ECR, R, S, D, or NE glasses, or the like; sulfides such
as molybdenum sulfide, zinc sulfide or the like; barium compounds
such as barium titanate, barium ferrite, barium sulfate, heavy
spar, or the like; metals and metal oxides such as particulate or
fibrous aluminum, bronze, zinc, copper and nickel or the like;
flaked fillers such as glass flakes, flaked silicon carbide,
aluminum diboride, aluminum flakes, steel flakes or the like;
fibrous fillers, for example short inorganic fibers such as those
derived from blends comprising at least one of aluminum silicates,
aluminum oxides, magnesium oxides, and calcium sulfate hemihydrate
or the like; natural fillers and reinforcements, such as wood flour
obtained by pulverizing wood, fibrous products such as cellulose,
cotton, sisal, jute, starch, cork flour, lignin, ground nut shells,
corn, rice grain husks or the like; organic fillers such as
polytetrafluoroethylene; reinforcing organic fibrous fillers formed
from organic polymers capable of forming fibers such as poly(ether
ketone), polyimide, polybenzoxazole, poly(phenylene sulfide),
polyesters, polyethylene, aromatic polyamides, aromatic polyimides,
polyetherimides, polytetrafluoroethylene, acrylic resins,
poly(vinyl alcohol) or the like; as well as additional fillers and
reinforcing agents such as mica, clay, feldspar, flue dust,
fillite, quartz, quartzite, perlite, tripoli, diatomaceous earth,
carbon black, or the like, or combinations comprising at least one
of the foregoing fillers or reinforcing agents.
[0153] In one aspect, a filler, if present, can be coated with a
layer of metallic material to facilitate conductivity, or surface
treated with silanes to improve adhesion and dispersion with the
polymeric matrix resin. In addition, the reinforcing fillers can be
provided in the form of monofilament or multifilament fibers and
can be used individually or in combination with other types of
fiber, such as, for example, co-weaving or core/sheath,
side-by-side, orange-type or matrix and fibril constructions, or by
other methods known to one skilled in the art of fiber manufacture.
Exemplary co-woven structures include, for example, glass
fiber-carbon fiber, carbon fiber-aromatic polyimide (aramid) fiber,
and aromatic polyimide fiberglass fiber or the like. Fibrous
fillers can be supplied in the form of, for example, rovings, woven
fibrous reinforcements, such as 0-90 degree fabrics or the like;
non-woven fibrous reinforcements such as continuous strand mat,
chopped strand mat, tissues, papers and felts or the like; or
three-dimensional reinforcements such as braids.
[0154] In one aspect, the filler is a reinforcing fiber. In a
further aspect, the reinforcing fiber comprises glass fiber.
Suitable glass fibers include glass fibers having a diameter of 2
to 16 micrometers and an average length, prior to melt mixing with
the other components, of 4 to 16 millimeters. The glass fiber can
be present in an amount of about 1 wt % to about 25 wt %, based on
the total weight of the composition. Within this range the amount
of glass fiber can be greater than or equal to about 1 wt %. In a
further aspect, the glass fiber is present in an amount greater
than or equal to about 5 wt %. Also within this range, the glass
fiber can be present in an amount less than or equal to about 20 wt
%. In a further aspect, the glass fiber is present in an amount
less than or equal to about 17 wt %. In a further aspect, the glass
fiber is present in an amount less than or equal to about 15 wt
%.
[0155] In various further aspects, the glass fiber is present in an
amount of about 5 wt % to about 15 wt %. In a still further aspect,
the glass fiber is present in an amount of about 7.5 wt % to about
12.5 wt %. In a yet further aspect, the glass fiber is present in
an amount of about 5 wt %. In an even further aspect, the glass
fiber is present in an amount of about 6 wt %. In a still further
aspect, the glass fiber is present in an amount of about 7 wt %. In
a yet further aspect, the glass fiber is present in an amount of
about 8 wt %. In an even further aspect, the glass fiber is present
in an amount of about 9 wt %. In a still further aspect, the glass
fiber is present in an amount of about 10 wt %. In a yet further
aspect, the glass fiber is present in an amount of about 11 wt %.
In an even further aspect, the glass fiber is present in an amount
of about 12 wt %. In a still further aspect, the glass fiber is
present in an amount of about 13 wt %. In a yet further aspect, the
glass fiber is present in an amount of about 14 wt %. In an even
further aspect, the glass fiber is present in an amount of about 15
wt %.
J. OTHER ADDITIVES FOR BLENDED POLYMER COMPOSITIONS
[0156] In other aspects, the inventive blended polymer compositions
can comprise one or more other materials that can maintain and/or
improve various properties of the resulting material. In various
aspects, the inventive blended polymer compositions can comprise a
lubricant, mold release agent, an anti-oxidant, a processing
stabilizer, a melt viscosity modifier, or a combination
thereof.
[0157] In addition to the thermally conductive additive, the
blended polymer composition can include various additives
ordinarily incorporated in resin compositions of this type, with
the proviso that the additives are selected so as to not
significantly adversely affect the desired properties of the
thermoplastic composition. Combinations of additives can be used.
Such additives can be mixed at a suitable time during the mixing of
the components for forming the composition.
[0158] In other aspects, a blended polymer composition can comprise
one or more of an antioxidant, flame retardant, heat stabilizer,
light stabilizer, UV absorbing additive, plasticizer, lubricant,
mold release agent, antistatic agent, colorant (e.g., pigment
and/or dye), or a combination thereof.
[0159] In various aspects, the blended polymer compositions of the
present invention comprise one or more antioxidants. Examples of
antioxidants useful in the present invention include, but are not
limited to, hindered phenols such
tetrakis[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]-methane,
4,4'-thiobis(2-methyl-6-tert-butylphenol), and thiodiethylene
bis(3,5-di-tert-butyl-4-hydroxy)hydrocinnamate, octadecyl-3
(3,5-di-tert.butyl-4-hydroxyphenyl)proprionate, pentaerythritol
tetrakis(3(3,5-di-tert.butyl-4-hydroxyphenyl)proprionate),
phosphites and phosphonites such as
tris(2,4-di-tert-butylphenyl)phosphite and thio compounds such as
dilaurylthiodipropionate, dimyristylthiodipropionate, and
distearylthiodipropionate, potassium iodide, cuprous iodide,
various siloxanes, and amines such as polymerized
2,2,4-trimethyl-1,2-dihydroquinoline and the like, or a combination
containing at least one of the foregoing.
K. METHODS FOR MAKING THERMALLY CONDUCTIVE, FLAME-RETARDANT BLENDED
POLYMER COMPOSITIONS
[0160] In one aspect, the invention relates to a method of
improving the flame retardancy of a thermally conductive polymer
composition, the method comprising the step of combining: from
about 20 wt % to about 60 wt % of an organic polymer selected from
polyamide, polyester, and polyolefin; from about 30 wt % to about
70 wt % of a thermal conductive additive selected from magnesium
hydroxide or aluminum oxide hydroxide; and from about 1 wt % to
about 10 wt % of a polyarylene sulfide; wherein all weight percent
values are based on the total weight of the composition; wherein
the composition exhibits a flame retardancy greater than that of an
otherwise identical composition without the polyarylene sulfide. In
a further aspect, the polyarylene sulfide is polyphenylene
sulfide.
[0161] In a further aspect, the method further comprises including
from about 1 wt % to about 30 wt % of a reinforcing filler. In a
further aspect, the method further comprises including a
high-thermal conductive filler. In a further aspect, the method
further comprises including an additive selected from coupling
agents, antioxidants, mold release agents, UV absorbers, light
stabilizers, heat stabilizers, lubricants, plasticizers, pigments,
dyes, colorants, anti-static agents, nucleating agents, anti-drip
agents, acid scavengers, and combinations of two or more of the
foregoing. In a further aspect, the combining step comprises adding
the polyarylene sulfide to a mixture of the organic polymer and the
magnesium hydroxide or boehmite (.gamma.-AlO(OH)).
[0162] In various aspects, the blended polymer compositions of the
present invention can be manufactured by various methods. The
compositions of the present invention can be blended with the
aforementioned ingredients by a variety of methods involving
intimate admixing of the materials with any additional additives
desired in the formulation. Because of the availability of melt
blending equipment in commercial polymer processing facilities,
melt processing methods can be used. In various further aspects,
the equipment used in such melt processing methods includes, but is
not limited to, the following: co-rotating and counter-rotating
extruders, single screw extruders, co-kneaders, disc-pack
processors and various other types of extrusion equipment. In a
further aspect, the extruder is a twin-screw extruder. In various
further aspects, the melt processed composition exits processing
equipment such as an extruder through small exit holes in a die.
The resulting strands of molten resin are cooled by passing the
strands through a water bath. The cooled strands can be chopped
into small pellets for packaging and further handling.
[0163] The temperature of the melt is minimized in order to avoid
excessive degradation of the resins. For example, it can be
desirable to maintain the melt temperature between about
230.degree. C. and about 350.degree. C. in the molten resin
composition, although higher temperatures can be used provided that
the residence time of the resin in the processing equipment is kept
short. In a still further aspect, the extruder is typically
operated at a temperature of about 180.degree. C. to about
385.degree. C. In a yet further aspect, the extruder is typically
operated at a temperature of about 200.degree. C. to about
330.degree. C. In an even further aspect, the extruder is typically
operated at a temperature of about 220.degree. C. to about
300.degree. C.
[0164] In various aspects, the blended polymer compositions of the
present invention can be prepared by blending the first polymer,
the second polymer, the impact modifier, the flow promoter, the
flame retardant, and any polymer composition additive, e.g. a
HENSCHEL-Mixer.RTM. high speed mixer or other suitable
mixer/blender. Other low shear processes, including but not limited
to hand mixing, can also accomplish this blending. The mixture can
then be fed into the throat of a single or twin screw extruder via
a hopper. Alternatively, at least one of the components can be
incorporated into the composition by feeding directly into the
extruder at the throat and/or downstream through a sidestuffer.
Additives can also be compounded into a masterbatch desired
polymeric resin and fed into the extruder. The extruder generally
operated at a temperature higher than that necessary to cause the
composition to flow. The extrudate is immediately quenched in a
water bath and pelletized. The pellets, so prepared, when cutting
the extrudate can be one-fourth inch long or less as desired. Such
pellets can be used for subsequent molding, shaping, or
forming.
[0165] In various aspects, the preparation of the blended polymer
compositions can be achieved by blending the ingredients under
conditions for the formation of an intimate blend. All of the
ingredients may be added initially to the processing system, or
else certain additives may be precompounded. The blend may be
formed by mixing in single or twin screw type extruders or similar
mixing devices that can apply a shear to the components, for
example Bush co-kneaders, Banbury mixers and Brabender mixers or an
injection molding compounding (IMC) process.
[0166] In various further aspects, separate extruders are used in
the processing of the blend. In a further aspect, the composition
is prepared by using a single extruder having multiple feed ports
along its length to accommodate the addition of the various
components. A vacuum may be applied to the melt through at least
one or more vent ports in the extruder to remove volatile
impurities in the composition. In a still further aspect, the
graphite particles can be feed downstream of the other blend
components.
L. ARTICLES
[0167] In one aspect, the invention relates to an extruded or
injection molded article, comprising the product of extrusion
molding or injection molding a composition comprising: from about
20 wt % to about 60 wt % of an organic polymer selected from
polyamide, polyester, and polyolefin; from about 30 wt % to about
70 wt % of a thermal conductive additive selected from magnesium
hydroxide or aluminum oxide hydroxide; and from about 1 wt % to
about 10 wt % of a polyarylene sulfide; wherein all weight percent
values are based on the total weight of the composition; wherein
the composition exhibits a flame retardancy greater than that of an
otherwise identical composition without the polyarylene
sulfide.
[0168] In a further aspect, the article further comprises from
about 1 wt % to about 30 wt % of a reinforcing filler. In a further
aspect, the reinforcing filler is glass fiber. In a further aspect,
the article further comprises a high-thermal conductive filler.
[0169] In a further aspect, the polyarylene sulfide comprises a
plurality of structural units of the formula:
##STR00008##
wherein for each structural unit, each Q.sup.1 and each Q.sup.2 is
independently hydrogen, halogen, primary or secondary lower alkyl,
phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or
halohydrocarbonoxy wherein at least two carbon atoms separate the
halogen and oxygen atoms.
[0170] In a further aspect, the polyarylene sulfide is
polyphenylene sulfide. In a further aspect, the article further
comprises an additive selected from coupling agents, antioxidants,
mold release agents, UV absorbers, light stabilizers, heat
stabilizers, lubricants, plasticizers, pigments, dyes, colorants,
anti-static agents, nucleating agents, anti-drip agents, acid
scavengers, and combinations of two or more of the foregoing. In a
further aspect, the composition exhibits a V0 compliant flame
retardancy.
[0171] In various aspects, the disclosed blended polymer
compositions with improved flame resistance of the present
invention can be used in making articles. The disclosed blended
polymer compositions can be formed into useful shaped articles by a
variety of means such as; injection molding, extrusion, rotational
molding, compression molding, blow molding, sheet or film
extrusion, profile extrusion, gas assist molding, structural foam
molding and thermoforming. The blended polymer compositions
described herein resins can also be made into film and sheet as
well as components of laminate systems. In a further aspect, a
method of manufacturing an article comprises melt blending the
char-forming polymer, the organic polymer, and the other disclosed
components; and molding the extruded composition into an article.
In a still further aspect, the extruding is done with a single
screw extruder or a twin screw extruder.
[0172] In various aspects, the formed articles of the present
invention comprise one or more of the following: automotive body
panels, computer and business machine housings, hand held
electronic device housings, electrical connectors, components of
lighting fixtures, ornaments, home appliances, roofs, greenhouses,
sun rooms, or swimming pool enclosures, safety door locking
systems, heat systems and radiators, shutters, accessories for
fences and posts. In a still further aspect, the articles of the
present invention are selected from a solar cell, solar cell
housing, or an electronic article, e.g. an LED, drive housing, or
contact housing. In a yet further aspect, the blended polymer
compositions of the present invention can be used in
self-controlled heaters, overcurrent protection devices, air
conditioning units, automotive applications, such as heated seats,
heated mirrors, heated windows, heated steering wheels, and the
like, circuit protection devices, perfume dispensers and any other
application in which a flame-retardant, thermally conductive
polymer blend can be used.
[0173] In various further aspects, examples of articles that maybe
made using the compositions of the present invention include, but
are not limited to, automotive body panels, computer and business
machine housings such as housings for monitors, hand held
electronic device housings such as housings for cell phones,
electrical connectors, and components of lighting fixtures,
ornaments, home appliances, roofs, greenhouses, sun rooms, swimming
pool enclosures, safety door locking systems, heat systems and
radiators, shutters, accessories for fences and posts, and the
like.
[0174] Formed articles include, for example, computer and business
machine housings, home appliances, trays, plates, handles, helmets,
automotive parts such as instrument panels, cup holders, glove
boxes, interior coverings and the like. In various further aspects,
formed articles include, but are not limited to, food service
items, medical devices, animal cages, electrical connectors,
enclosures for electrical equipment, electric motor parts, power
distribution equipment, communication equipment, computers and the
like, including devices that have molded in snap fit connectors. In
a further aspect, articles of the present invention comprise
exterior body panels and parts for outdoor vehicles and devices
including automobiles, protected graphics such as signs, outdoor
enclosures such as telecommunication and electrical connection
boxes, and construction applications such as roof sections, wall
panels and glazing. Multilayer articles made of the disclosed
polymers particularly include articles which will be exposed to
UV-light, whether natural or artificial, during their lifetimes,
and most particularly outdoor articles; i.e., those intended for
outdoor use. Suitable articles are exemplified by enclosures,
housings, panels, and parts for outdoor vehicles and devices;
enclosures for electrical and telecommunication devices; outdoor
furniture; aircraft components; boats and marine equipment,
including trim, enclosures, and housings; outboard motor housings;
depth finder housings, personal water-craft; jet-skis; pools; spas;
hot-tubs; steps; step coverings; building and construction
applications such as glazing, roofs, windows, floors, decorative
window furnishings or treatments; treated glass covers for
pictures, paintings, posters, and like display items; wall panels,
and doors; protected graphics; outdoor and indoor signs;
enclosures, housings, panels, and parts for automatic teller
machines (ATM); enclosures, housings, panels, and parts for lawn
and garden tractors, lawn mowers, and tools, including lawn and
garden tools; window and door trim; sports equipment and toys;
enclosures, housings, panels, and parts for snowmobiles;
recreational vehicle panels and components; playground equipment;
articles made from plastic-wood combinations; golf course markers;
utility pit covers; computer housings; desk-top computer housings;
portable computer housings; lap-top computer housings; palm-held
computer housings; monitor housings; printer housings; keyboards;
facsimile machine housings; copier housings; telephone housings;
mobile phone housings; radio sender housings; radio receiver
housings; light fixtures; lighting appliances; network interface
device housings; transformer housings; air conditioner housings;
cladding or seating for public transportation; cladding or seating
for trains, subways, or buses; meter housings; antenna housings;
cladding for satellite dishes; coated helmets and personal
protective equipment; coated synthetic or natural textiles; coated
photographic film and photographic prints; coated painted articles;
coated dyed articles; coated fluorescent articles; coated foam
articles; and like applications.
[0175] In one aspect, the present invention pertains to articles
comprising the disclosed blended polymer compositions. In a further
aspect, the article comprising the disclosed blended polymer
compositions is used in automotive applications. In a still further
aspect, the article used in automotive applications is selected
from instrument panels, overhead consoles, interior trim, center
consoles, panels, quarter panels, rocker panels, trim, fenders,
doors, deck lids, trunk lids, hoods, bonnets, roofs, bumpers,
fascia, grilles, minor housings, pillar appliques, cladding, body
side moldings, wheel covers, hubcaps, door handles, spoilers,
window frames, headlamp bezels, headlamps, tail lamps, tail lamp
housings, tail lamp bezels, license plate enclosures, roof racks,
and running boards. In a yet further aspect, the article used in
automotive applications is selected from seats, seat backs, cargo
floors, door panels, steering wheels, radio speaker grilles,
instrument panel bezels, steering columns, drip rails, energy
absorbers, kick panels, mirror housings, grille opening
reinforcements, steps, hatch covers, knobs, buttons, and levers. In
an even further aspect, the article used in automotive applications
is selected from seats, seat backs, cargo floors, door panels,
steering wheels, radio speaker grilles, instrument panel bezels,
steering columns, drip rails, energy absorbers, kick panels, mirror
housings, grille opening reinforcements, steps, hatch covers,
knobs, buttons, and levers. In an even further aspect, article is
selected from instrument panels, overhead consoles, interior trim,
center consoles, panels, quarter panels, rocker panels, trim,
fenders, doors, deck lids, trunk lids, hoods, bonnets, roofs,
bumpers, fascia, grilles, minor housings, pillar appliques,
cladding, body side moldings, wheel covers, hubcaps, door handles,
spoilers, window frames, headlamp bezels, headlamps, tail lamps,
tail lamp housings, tail lamp bezels, license plate enclosures,
roof racks, running boards, seats, seat backs, cargo floors, door
panels, steering wheels, radio speaker grilles, instrument panel
bezels, steering columns, drip rails, energy absorbers, kick
panels, mirror housings, grille opening reinforcements, steps,
hatch covers, knobs, buttons, and levers.
[0176] Without further elaboration, it is believed that one skilled
in the art can, using the description herein, utilize the present
invention. The following examples are included to provide addition
guidance to those skilled in the art of practicing the claimed
invention. The examples provided are merely representative of the
work and contribute to the teaching of the present invention.
Accordingly, these examples are not intended to limit the invention
in any manner.
[0177] While aspects of the present invention can be described and
claimed in a particular statutory class, such as the system
statutory class, this is for convenience only and one of skill in
the art will understand that each aspect of the present invention
can be described and claimed in any statutory class. Unless
otherwise expressly stated, it is in no way intended that any
method or aspect set forth herein be construed as requiring that
its steps be performed in a specific order. Accordingly, where a
method claim does not specifically state in the claims or
descriptions that the steps are to be limited to a specific order,
it is no way intended that an order be inferred, in any respect.
This holds for any possible non-express basis for interpretation,
including matters of logic with respect to arrangement of steps or
operational flow, plain meaning derived from grammatical
organization or punctuation, or the number or type of aspects
described in the specification.
[0178] Throughout this application, various publications are
referenced. The disclosures of these publications in their
entireties are hereby incorporated by reference into this
application in order to more fully describe the state of the art to
which this pertains. The references disclosed are also individually
and specifically incorporated by reference herein for the material
contained in them that is discussed in the sentence in which the
reference is relied upon. Nothing herein is to be construed as an
admission that the present invention is not entitled to antedate
such publication by virtue of prior invention. Further, the dates
of publication provided herein may be different from the actual
publication dates, which can require independent confirmation.
Examples
[0179] The following examples are put forth so as to provide those
of ordinary skill in the art with a complete disclosure and
description of how the compounds, compositions, articles, devices
and/or methods claimed herein are made and evaluated, and are
intended to be purely exemplary and are not intended to limit the
disclosure. Efforts have been made to ensure accuracy with respect
to numbers (e.g., amounts, temperature, etc.), but some errors and
deviations should be accounted for. Unless indicated otherwise,
parts are parts by weight, temperature is in .degree. C. or is at
ambient temperature, and pressure is at or near atmospheric. Unless
indicated otherwise, percentages referring to composition are in
terms of wt %.
[0180] There are numerous variations and combinations of reaction
conditions, e.g., component concentrations, desired solvents,
solvent mixtures, temperatures, pressures and other reaction ranges
and conditions that can be used to optimize the product purity and
yield obtained from the described process. Only reasonable and
routine experimentation will be required to optimize such process
conditions.
[0181] Flame retardant properties were determined in accordance
with UL-94 guidelines on calibrated equipment. Samples were
conditioned at 23.degree. C. and 50% relative humidity prior to
analysis. For the UL-94 V-0 rating, the maximum total burn time is
50 seconds. In the examples below, a pass rating is indicated if
the maximum burn time was 50 seconds or less.
[0182] Through-plane and in-plane thermal conductivity were
measured on a HotDisk TPS2500 apparatus according to ISO 22007-2 on
100.times.3 mm discs. A 6 mm radius sensor was used in anisotropic
method mode. All measurements were performed under controlled
conditions (23.degree. C. and 50% relative humidity). Bulk thermal
conductivity was calculated as follows, wherein "thermal
conductivity" is indicated by "TC":
BulkTC= {square root over
(TC.sub.through-plane.times.TC.sub.in-plane)}
[0183] The materials shown in Table 1 were used to prepare the
compositions described herein. Melt processing (compounding and
extrusion) was carried out using a vacuum vented ZSK 25 (ZSK
25P8,2; Coperion Gmbh, formerly Coperion Werner & Pfleiderer,
Stuttgart, Germany) twin-screw extruder having a screw diameter of
about 25 mm and L/D of about 40:1. The ZSK 25 was operated with a
4*4(4 holes, each with a 4 mm diameter) die lip and with four
independent feeders for different raw materials (feeder 1 & 4
at section 1, feeder 2 at section 4 and feeder 3 at section 6; see
FIG. 1 for a diagram showing the layout of the various feeder and
sections of the machine) and using the compounding profile
conditions as shown in Table 2.
TABLE-US-00001 TABLE 1 Abbre- viation Description Source PA1
Polyamide 6 produced from caprolactam; DOMOChemicals commercially
available as Domamid .RTM. 24 with an intrinsic viscosity of about
2.4. PA2 Polyamide 6 produced from caprolactam; DOMO commercially
available as Domamid .RTM. 27 Chemicals with an intrinsic viscosity
of about 2.7. MG Mg(OH).sub.2 with a particle size, d.sub.90, of
Albemarle about 2.40-4.40 .mu.m and a specific Corporation surface
area of about 4.0-6.0 m.sup.2/g; commercially available as Magnifin
H5 IV. GF Chopped strand glass fibers comprising PPG E-Glass (ASTM
D 578-98, paragraph 4.2.2) with a nominal fiber diameter of 10
.mu.m and a standard cut length of 4.5 mm; available as ChopVantage
.RTM. HP 3660. GRPH Graphite; commercially available as Asbury
Carbons Graphite 2012, which is a Sri Lankan type of natural
graphite, with % Carbon (LOI) of 97~100, with at least 92 wt % of
graphite having diameter between 44 and 300 micro-meter. PETS
Pentaerythritol tetrastearate with a maximum Lonza Benelux
saponification value of about 195 and a B.V. maximum hydroxyl
number of about 12; commercially available as Glycolube P AO1
Primary antioxidant; sterically hindered BASF phenolic antioxidant,
N,N'-hexamethylene bis[3-(3,5-di-t-butyl-4 -hydroxy-
phenyl)propionamide]; commercially available as Irganox 1098. AO2
Antioxidant; tris(2,4-di-tert-butylphenyl) BASF phosphite;
commercially available as Irgafox 168. FM Polymeric chain extender
used to increase BASF melt viscosity; commercially available as
Joncryl .RTM. ADR-4386-C, which is flake shaped processing additive
and can be used during processing to increase melt strength. PPS
Medium viscosity polyphenylene sulfide Ticona Gmbh with a glass
transition temperature, T.sub.g, of about 90.0.degree. C. when
determined in accordance with ISO 11357, and a coefficient of
thermal expansion (linear, parallel to flow) of about53.0
.mu.m/m-.degree. C. when determined in accordance with ISO 11359;
commercially available as Fortran .RTM. 0205 B4
TABLE-US-00002 TABLE 2 Description Unit Range Setting Zone 1 Temp
(intake) .degree. C. not adjustable n.a. Zone 2 Temp .degree. C.
0-380 150 Zone 3 Temp .degree. C. 0-380 220 Zone 4 Temp .degree. C.
0-380 250 Zone 5 Temp .degree. C. 0-380 260 Zone 6 Temp .degree. C.
0-380 260 Zone 7 Temp .degree. C. 0-380 260 Zone 8 Temp .degree. C.
0-380 260 Zone 9 Temp .degree. C. 0-380 260 Zone 10 Temp .degree.
C. 0-380 265 Zone 11 Temp (die) .degree. C. 0-380 275 Zone 12 Temp
.degree. C. n.a. 255 Die Temp .degree. C. SeeZone 11 -- Screw Speed
rpm 120-1200 300 Torque %* -- 60-70 *% of maximum torque of the
machine; maximum torque is 164 N m
[0184] Test parts were injection molded on an Engel 70T-molding
according to the conditions shown in Table3. The pellets were dried
for 4 hours at 80.degree. C. in a forced air-circulating oven prior
to injection molding. Different molds were used, including UL-bars
of different thicknesses and 3 mm thick disks with a diameter of 85
mm.
TABLE-US-00003 TABLE 3 Parameter Unit Value Drying time hr 4 Drying
temperature .degree. C. 80 T hopper .degree. C. 40 T zone 1
.degree. C. 270 T zone 2 .degree. C. 280 T zone 3 .degree. C. 290 T
nozzle .degree. C. 295 T mold .degree. C. 90
[0185] The formulations for representative compositions of the
present invention (Examples 1-9) are given in Tables 4 and 5, and
thermal and flame characteristics are provided in Tables 6 and 7.
Comparative Examples, which are labeled as C1-C9, are shown in
these same tables.
[0186] The data in Table 6 show that when the Mg(OH).sub.2 content
was 40 wt %, flame-out times are relatively long and combined with
the observed burning drips a V2 rating is obtained for comparative
example C1. Upon addition of PPS flame-out times increases and the
flammability rating decreases from V2 to NR (non-rated).
[0187] Increasing the Mg(OH).sub.2 loading to 47.5 wt % still
yielded V2 ratings at all tested thicknesses for the comparative
sample (C2). Addition of PPS did not improve the flammability
rating for thickness of 1.5 mm and lower, in fact ratings dropped
from V2 to non-rated, again due to increased flame-out times.
However, it was observed that addition of PPS reduced the tendency
for dripping at thicknesses of 1.0 mm and above. Moreover, a
positive effect upon addition of >4 wt % of PPS resin on
flammability rating was observed when sample thickness increased to
2.0 mm, e.g. the data in Table 6 show that the flammability rating
improved from NR (example C2) to V1 for 2.0 mm thick samples.
[0188] The data clearly show the positive effect of PPS addition at
even higher Mg(OH).sub.2 loadings, e.g. see comparative examples
C3, C4 and C5 compared to examples #5 to #9 in Table 6. The
addition of PPS leads to greater charring and decreased dripping
resulting in an improvement of the UL-94 result at 1.0 mm from V2
(comparative example C3) to V0 for formulations containing 49 wt %
Mg(OH).sub.2 (see example #5). Similar improvements were found at
55 wt % Mg(OH).sub.2 loading. For example, only V2 ratings were
obtained for 1.0 and 0.8 mm thick UL-bars with comparative example
C4. In contrast, addition of a small amount of PPS resin (2 wt %,
see example #6) improved the rating at 1.0 and 0.8 mm to V1 and
effectively prevented dripping. Increasing the PPS loading further
yielded a further improvement in the flammability rating to V0.
Comparative example C5 and example #9 show that addition of PPS
improves the flammability rating for formulations that do not
contain glass fiber. For example, addition of 6% of PPS improves
flammability rating from V2 to V0 at 2.0, 1.5 and 1.2 mm thickness
and from V2 to V1 at 1.0 mm thickness.
[0189] It is important to note that the addition of PPS does not
significantly affect the bulk thermal conductivity, which is
defined as the square root of the product of in-plane and through
plane thermal conductivity. Due to changes in viscosity, there are
some changes in through and in-plane thermal conductivity, but
typically any change in the thermal conductivity in plane is offset
by a roughly similar relative but opposite change in the
through-plane direction, as a result of which the bulk thermal
conductivity remains more or less constant.
[0190] The data in Table 7 show that when no PPS resin was present
(see comparative examples C6 and C7), the samples showed excessive
dripping (10 flaming drips out of 10 bars tested) at 1.5 and 1.2 mm
thicknesses. The addition of 2% PPS (see example #10) reduced the
number of burning drips by 50%, but the overall rating remained V2.
However, a V0 rating was obtained when the PPS content was
increased to 4 wt % or higher (see examples #11 and #12).
[0191] Oligomeric chain extenders, e.g. Joncryl-ADR-4368-C, are
common processing additives in compositions comprising polyamides
and polyarylene sulfides. For example, multi-functional epoxy
additives of this type can compatibilize the PPS and PA. A small
improvement in mechanical properties was observed (data not shown).
Without wishing to be bound by a particular theory, the epoxy
groups of the compatibilizing agent can react with both the
endgroups of the PPS as well as the PA, thus leading to
compatibilization. Alternatively, and again without wishing to be
bound by a particular theory, chain extension of the PA chains can
also occur. Both compatibilization as well as chain extension will
have a positive effect on mechanical properties. The comparative
example with an oligomeric chain extender, but without PPS (see
comparative example C8 in Table 7), showed extensive dripping
(burning drips) in the flammability test with a resultant V2 rating
at 1.5 and 1.2 mm thickness. However, addition of PPS (see examples
#13 and #14 in Table 7) eliminated dripping and resulted in an
improved flammability rating of V0.
[0192] The data in Table 7 show that the addition of PPS had a
positive effect on flammability in formulations comprising both
Mg(OH).sub.2 and graphite (see comparative example C9, example #15
and example #16). The data show that samples comprising PPS had a
V0 flammability rating whereas the comparative sample was
non-rated. There is a small negative effect observed in bulk
thermal conductivity in the samples comprising PPS, Mg(OH).sub.2,
and graphite, but the magnitude is relatively small and less than
10% of the initial value.
TABLE-US-00004 TABLE 4 Component* C1 #1 C2 #2 #3 #4 PA1 49.100
43.100 41.600 39.600 37.600 35.600 MG 40.000 40.000 47.500 47.500
47.500 47.500 GF 10.000 10.000 10.000 10.000 10.000 10.000 PETS
0.500 0.500 0.500 0.500 0.500 0.500 AO1 0.200 0.200 0.200 0.200
0.200 0.200 AO2 0.200 0.200 0.200 0.200 0.200 0.200 PPS -- 6.000 --
2.000 4.000 -- Component* C3 #5 C4 #6 #7 #8 PA1 35.600 40.100
34.100 34.100 32.100 30.100 MG 47.500 49.000 49.000 55.000 55.000
55.000 GF 10.000 10.000 10.000 10.000 10.000 10.000 PETS 0.500
0.500 0.500 0.500 0.500 0.500 AO1 0.200 0.200 0.200 0.200 0.200
0.200 AO2 0.200 0.200 0.200 0.200 0.200 0.200 PPS 6.000 -- 6.000 --
2.000 4.000 Component* C5 #9 PA1 44.100 38.100 MG 55.000 55.000 GF
-- -- PETS 0.500 0.500 AO1 0.200 0.200 AO2 0.200 0.200 PPS -- 6.000
*See TABLE 1 for description of components.
TABLE-US-00005 TABLE 5 Component* C6 C7 #10 #11 #12 C8 PA1 36.60 --
34.60 32.60 28.60 36.60 PA2 -- 36.60 -- -- -- -- MG 45.10 45.10
45.10 45.10 45.10 45.10 GRPH 17.45 17.45 17.45 17.45 17.45 17.45
PETS 0.50 0.50 0.50 0.50 0.50 0.50 AO1 0.20 0.20 0.20 0.20 0.20
0.20 AO2 0.15 0.15 0.15 0.15 0.15 0.15 FM -- -- -- -- -- -- PPS --
-- 2.00 4.00 8.00 -- Component* #13 #14 C9 #15 #16 PA1 28.35 28.10
34.55 30.55 28.55 PA2 -- -- -- -- -- MG 45.10 45.10 52.6 52.6 52.6
GRPH 17.45 17.45 12 12 12 PETS 0.50 0.50 0.5 0.5 0.5 AO1 0.20 0.20
0.2 0.2 0.2 AO2 0.15 0.15 0.15 0.15 0.15 FM 0.25 0.50 -- -- -- PPS
8.00 8.00 -- 4.00 6.00 *See TABLE 1 for description of
components.
TABLE-US-00006 TABLE 6 Test* Unit C1 #1 C2 #2 #3 #4 UL-94, 2.0 mm
-- V2 NR NR NR V1 V1 UL-94, 1.5 mm -- V2 NR V2 NR NR NR UL-94, 1.2
mm -- V2 NR V2 NR NR NR UL-94, 1.0 mm -- V2 NR V2 NR NR NR UL-94,
0.8 mm -- V2 V2 V2 NR NR NR Thermal W/mK 0.72 0.76 0.89 0.93 0.73
0.66 Conductivity - Hot disk through-plan Thermal W/mK 0.83 0.78
0.96 1.00 1.25 1.32 Conductivity - Hot disk in- plan Thermal W/mK
0.77 0.77 0.92 0.96 0.96 0.93 conductivity - bulk thermal
conductivity Test* Unit C3 #5 C4 #6 #7 #8 UL-94, 2.0 mm -- n.d.
n.d. V0 V0 V0 V0 UL-94, 1.5 mm -- n.d. n.d. V0 V0 V0 V0 UL-94, 1.2
mm -- n.d. n.d. V0 V0 V0 V0 UL-94, 1.0 mm -- V2 V0 V2 V1 V0 V0
UL-94, 0.8 mm -- n.d. n.d. V2 V1 V0 V0 Thermal W/mK 0.90 0.76 0.95
0.95 0.76 0.90 Conductivity - Hot disk through-plan Thermal W/mK
1.06 1.26 1.31 1.45 1.74 1.06 Conductivity - Hot disk in- plan
Thermal W/mK 0.98 0.98 1.12 1.18 1.15 0.98 conductivity - bulk
thermal conductivity Test* Unit C5 #9 UL-94, 2.0 mm -- V2 V0 UL-94,
1.5 mm -- V2 V0 UL-94, 1.2 mm -- V2 V0 UL-94, 1.0 mm -- V2 V1
UL-94, 0.8 mm -- V2 V2 Thermal W/mK 0.83 0.78 Conductivity - Hot
disk through-plan Thermal W/mK 1.20 1.31 Conductivity - Hot disk
in- plan Thermal W/mK 1.00 1.01 conductivity - bulk thermal
conductivity *Conducted as described herein above; "n.d." indicates
"not determined" and "NR" indicates "non-rated."
TABLE-US-00007 TABLE 7 Test* Unit C6 C7 #10 #11 #12 C8 UL-94, 2.0
mm -- V0 n.d. n.d. n.d. n.d. n.d. UL-94, 1.5 mm -- V2 V2 V2 V0 V0
V2 UL-94, 1.2 mm -- V2 V2 V2 V0 V0 V2 UL-94, 1.0 mm -- n.d. n.d.
n.d. n.d. n.d. n.d. UL-94, 0.8 mm -- n.d. n.d. n.d. n.d. n.d. n.d.
Thermal W/mK 1.40 1.30 1.46 1.28 1.39 1.41 Conductivity - Hot disk
through-plan Thermal W/mK 3.67 4.00 3.30 3.82 3.32 3.90
Conductivity - Hot disk in- plan Thermal W/mK 2.27 2.28 2.19 2.21
2.15 2.35 conductivity - bulk thermal conductivity Test* Unit #13
#14 C9 #15 #16 UL-94, 2.0 mm -- n.d. n.d. n.d. n.d. n.d. UL-94, 1.5
mm -- V0 V0 n.d. n.d. n.d. UL-94, 1.2 mm -- V0 V0 n.d. n.d. n.d.
UL-94, 1.0 mm -- n.d. n.d. NR V0 V0 UL-94, 0.8 mm -- n.d. n.d. NR
V0 V0 Thermal W/mK 1.35 1.36 1.32 1.30 1.21 Conductivity - Hot disk
through-plan Thermal W/mK 3.31 3.64 3.30 3.18 3.51 Conductivity Hot
disk in- plan Thermal W/mK 2.12 2.23 2.09 2.03 2.06 conductivity -
bulk thermal conductivity *Conducted as described herein above;
"n.d." indicates "not determined" and "NR" indicates
"non-rated."
[0193] It will be apparent to those skilled in the art that various
modifications and variations can be made in the present invention
without departing from the scope or spirit of the invention. Other
embodiments of the invention will be apparent to those skilled in
the art from consideration of the specification and practice of the
invention disclosed herein. It is intended that the specification
and examples be considered as exemplary only, with a true scope and
spirit of the invention being indicated by the following
claims.
* * * * *